The synthesis and characterization of a series of cocrystals of an isoniazid derivative with butan-2-one and propan-2-one

Scheepers, M.C.; Lemmerer, A.

doi:10.1107/S2053229623007179

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 79| Part 9| September 2023| Pages 365-373

https://doi.org/10.1107/S2053229623007179

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The synthesis and characterization of a series of cocrystals of an isoniazid derivative with butan-2-one and propan-2-one

Matthew Clarke Scheepers ^a and Andreas Lemmerer ^a ^*

^aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, Johannesburg, Gauteng 2050, South Africa
^*Correspondence e-mail: andreas.lemmerer@wits.ac.za

Edited by L. Dawe, Wilfrid Laurier University, Waterloo, Ontario, Canada (Received 22 May 2023; accepted 15 August 2023; online 21 August 2023)

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

Four cocrystals containing N′-(butan-2-ylidene)pyridine-4-carbohydrazide (izbt) and one cocrystal containing N′-isopropylideneisonicotinohydrazide (izact) were synthesized by reacting isoniazid with either butan-2-one (for the former) or acetone (for the latter). The coformers used to synthesize the izbt cocrystals were 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2-chloro-4-nitrobenzoic acid and 1-naphthoic acid. 1-Naphthoic acid was also used with izact to form a cocrystal. The 1:1 cocrystals are: N′-(butan-2-ylidene)pyridine-4-carbohydrazide–1-naphthoic acid (izbt–1nta), C₁₀H₁₃N₃O·C₁₁H₈O₂, N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2,4-dihydroxybenzoic acid (izbt–2,4-dhba), C₁₀H₁₃N₃O·C₇H₆O₄, N′-(propan-2-ylidene)pyridine-4-carbohydrazide–1-naphthoic acid (izact–1nta), C₉H₁₁N₃O·C₁₁H₈O₂, N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2-chloro-4-nitrobenzoic acid (izbt–2c4n), C₁₀H₁₃N₃O·C₇H₄ClNO₄, and N′-(butan-2-ylidene)pyridine-4-carbohydrazide–2,5-dihydroxybenzoic acid (izbt–2,5-dhba), C₁₀H₁₃N₃O·C₇H₆O₄. The cocrystals containing izbt were compared to those containing the same (or similar) coformers with izact that have been reported either here or in the Cambridge Structural Database (CSD). Most of the cocrystals showed different packing despite having the same hydrogen-bonding motifs. The cocrystals were characterized by single-crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD) and differential scanning calorimetry (DSC).

Keywords: crystal structure; cocrystal; isoniazid; dicarboxylic acid; pyridine; carbohydrazide; naphthoic acid; thermal analysis.

CCDC references: 2264437; 2264438; 2264434; 2264436; 2264435

1. Introduction

In the pharmaceutical industry, it is often typical for new and existing drugs to have poor physicochemical properties. The poor performance from these drugs can hamper their success on the market. The modification of an existing drug can yield a new product with possibly improved properties compared to the original drug molecule. Although this would require new clinical trials, it could prove to be advantageous for long-term success. From a crystal engineering perspective, this could prove to be an opportunity to explore new solid-state structural landscapes.

One approach of crystal engineering with repsect to changing the solid-state form of active pharmaceutical ingredients (APIs) is to use cocrystals. Although no universal definition of a cocrystal exists, several different definitions have been proposed by different authors. The definition proposed by Aitipamula et al. (2012 ) is as follows: `cocrystals are solids that are crystalline single phase materials composed of two or more different molecular and/or ionic compounds generally in a stoichiometric ratio.' Grothe defines a cocrystal as `a crystal with a coformer molecule plus either another coformer or at least two ions,' with further classifications depending on whether the crystal also contains ions, solvate molecules or water (Grothe et al., 2016 ). Cocrystals have been proven to have new properties, such as having a different solubility or bioavailability over the starting material (Karimi-Jafari et al., 2018 ). It can even lead to the possibility of having multiple drugs in one crystal form (Wang et al., 2021 ). Unfortunately, cocrystal design and synthesis is not straightforward; it is possible to fail creating a cocrystal despite using a reasonable cocrystal design methodology (Bučar et al., 2013 ).

Isoniazid (inh) is an antibacterial drug used to treat Mycobacterium tuberculosis bacteria (TB). It is often combined with several different drugs in a fixed-dose combination (FDC) as part of the treatment for this disease (Murray et al., 2015 ). However, inh has been known to undergo degradation in the presence of other drugs (Bhutani et al., 2005 ). Inh is a fairly simple drug molecule, consisting of a pyridine ring, an amide group and a hydrazine group. One way to modify inh is to employ a Schiff base reaction using inh and either an aldehyde or a ketone. In previous work, we modified isoniazid with acetone, butan-2-one, 4-hydroxy-4-methylpentan-2-one and benzophenone, and explored a different number of cocrystal and molecular salt crystal structures (Lemmerer et al., 2010 ; Madeley et al., 2019 ; Scheepers & Lemmerer, 2022 ; Lemmerer, 2012 ). In particular, a decent number of cocrystals and molecular salts with isoniazid derived from acetone and butan-2-one have been reported, with seven crystal structures containing N′-(butan-2-ylidene)pyridine-4-carbohydrazide (butan-2-one-based derivative, izbt) and 15 containing N′-isopropylideneisonicotinohydrazide (acetone-based derivative, izact). Out of these, only five pairs share the same coformer, of which, three pairs are isostructural (Table 1). It should not be too surprising to find crystal structures becoming isostructural when certain functional groups are exchanged with a similar one, for example, changing a chlorine to a bromine or methyl to an amino group (Clarke et al., 2012 ). However, it is still possible that exchanging one functional group for another can yield a completely different structure. In the case of izact and izbt, the difference is the presence or absence of the methylene group in the alkyl group. In three of the cases, this had no effect, but in the case of the anyhydrous forms of izact– and izbt–3-hydroxybenzoic acid, and izact– and izbt–2-hydrobenzoic acid, there was a significant difference in the packing. Based on the structures listed in Table 1, we would expect that the methylene group would very likely have a small or even insignificant effect on the overall packing of the molecules in the crystal structure; however, with a small sample size it is difficult to assess if this is a reasonable assertion. Therefore, the aim of this work is to expand the number of multicomponent crystal structure pairs and compare them, in order to confirm whether the addition of the methylene group can have a significant impact of the packing of these structures. The simplest way to achieve this is to expand the number of izbt cocrystals using coformers that worked for izact; the coformers used include: 2,4-dihydroxybenzoic acid (2,4-dhba), 2,5-dihydroxybenzoic acid (2,5-dhba) and 2-chloro-4-nitrobenzoic acid (2c4n). In addition, cocrystals containing 1-naphthoic acid (1nta) with izact and izbt, respectively, were synthesized and characterized. 1nta was used to observe the effect of using a bulky double ring as opposed to using coformers consisting of a single ring. The structures of these compounds are represented in Scheme 1.

Table 1
Cocrystals of izact and izbt that share the same coformer

The Crystal Structure Similarity tool of Mercury (Macrae et al., 2020) was used to help determine if related structures were isostructural.

Coformer	izact refcode	izbt refcode	Isostructural
4-tert-Butylbenzoic acid	GIYMAF	GIYMEJ	Yes
2-Hydroxybenzoic acid (salicylic acid)*	LATLAV	UBILAW	No
3-Hydroxybenzoic acid (anhydrous)	FADHUP	FADHOJ	No
3-Hydroxybenzoic acid hydrate	SAYPIT	SAYPOZ	Yes
4-Nitrobenzoic acid	XOPYEJ	XOPYUZ	Yes
Note: (*) it should be noted that the unit-cell parameters of both structures are similar but the orientations of the molecules with respect to the unit cells differ significantly.

2. Experimental

2.1. Materials

All materials were purchased from Sigma–Aldrich and were used without further purification.

2.2. General procedure for the synthesis of izbt and izact cocrystals

The general procedure for synthesizing cocrystals featuring either izbt or izact is as follows: stoichiometric ratios of inh and the respective coformer (1:1 ratio) were dissolved in absolute ethanol (5 ml) in a small vial. The deriving ketone (acetone or butan-2-one) (1 ml) was added. This vial was closed and the mixture stirred for 4 h. Afterwards, the lid on the vial was replaced with a lid with a hole in it and the vial kept in a dark cupboard. After several days, crystals remained after the solvent evaporated.

2.3. Powder X-ray diffraction (PXRD)

PXRD was used to determine the bulk phase purity of each sample. PXRD data for all forms were measured at 293 K on a Bruker D2 Phaser diffractometer which employs a sealed tube Co X-ray source (λ = 1.78896 Å), operating at 30 kV and 10 mA, and a LynxEye PSD detector in Bragg–Brentano geometry. The powder patterns for the cocrystals are presented in the supporting information, where the experimentally measured pattern is compared to the calculated patterns obtained from the single-crystal X-ray diffraction (SC-XRD) data, as well as the calculated patterns of its components using data from the Cambridge Structural Database (CSD, Version 2022.1.0; Groom et al., 2016 ).

2.4. Single-crystal X-ray diffraction (SC-XRD) and refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All carbon-bound H atoms were placed in idealized positions and refined as riding atoms, with U_iso(H) parameters 1.2 or 1.5 times those of the parent atoms. Most nitrogen- and oxygen-bound H atoms were located in difference Fourier maps, and their coordinates and isotropic displacement parameters were refined freely.

Table 2
Experimental details

For all structures: Z = 4. Experiments were carried out with Mo Kα radiation using a Bruker D8 VENTURE PHOTON CMOS 100 area-detector diffractometer.

	izbt–1nta	izbt–2,4-dhba	izact–1nta
Crystal data
Chemical formula	C₁₀H₁₃N₃O·C₁₁H₈O₂	C₁₀H₁₃N₃O·C₇H₆O₄	C₉H₁₁N₃O·C₁₁H₈O₂
M_r	363.41	345.35	349.38
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, Cc
Temperature (K)	173	173	173
a, b, c (Å)	7.4355 (13), 34.195 (6), 7.7242 (14)	11.0834 (6), 13.8364 (8), 12.0014 (7)	7.6312 (3), 33.5293 (12), 7.3493 (3)
α, β, γ (°)	90, 112.512 (4), 90	90, 115.710 (3), 90	90, 114.298 (1), 90
V (Å³)	1814.3 (6)	1658.26 (17)	1713.88 (12)
μ (mm⁻¹)	0.09	0.10	0.09
Crystal size (mm)	0.34 × 0.28 × 0.12	0.32 × 0.25 × 0.21	0.72 × 0.33 × 0.08

Data collection
Absorption correction	–	–	Multi-scan (SADABS; Sheldrick, 2001 ; Krause et al., 2015 )
T_min, T_max	–	–	0.684, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	35501, 4511, 3552	25708, 4008, 1946	39441, 6819, 6145
R_int	0.033	0.092	0.056
(sin θ/λ)_max (Å⁻¹)	0.668	0.660	0.782

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.142, 1.03	0.061, 0.219, 1.02	0.043, 0.122, 1.08
No. of reflections	4511	4008	6819
No. of parameters	254	248	238
No. of restraints	0	39	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.34	0.70, −0.27	0.33, −0.17
Absolute structure	–	–	Flack x determined using 2626 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	–	–	0.0 (3)

	izbt–2c4n	izbt–2,5-dhba
Crystal data
Chemical formula	C₇H₄ClNO₄·C₁₀H₁₃N₃O	C₁₀H₁₃N₃O·C₇H₆O₄
M_r	392.79	345.35
Crystal system, space group	Monoclinic, P2₁/n	Triclinic, P $[\overline{1}]$
Temperature (K)	173	123
a, b, c (Å)	7.2682 (3), 34.0775 (15), 7.6124 (3)	9.2054 (3), 11.5589 (4), 15.6268 (6)
α, β, γ (°)	90, 111.081 (2), 90	92.383 (2), 93.092 (2), 90.666 (2)
V (Å³)	1759.27 (13)	1658.74 (10)
μ (mm⁻¹)	0.26	0.10
Crystal size (mm)	0.46 × 0.26 × 0.11	0.45 × 0.38 × 0.13

Data collection
No. of measured, independent and observed [I > 2σ(I)] reflections	111394, 5624, 5056	73254, 8026, 5972
R_int	0.081	0.079
(sin θ/λ)_max (Å⁻¹)	0.726	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.129, 1.07	0.068, 0.191, 1.04
No. of reflections	5624	8026
No. of parameters	250	506
No. of restraints	0	21
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.28	1.33, −0.68
Computer programs: APEX2 (Bruker, 2012 ), SAINT-Plus (Bruker, 2012), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020), ORTEP-3 for Windows (Farrugia, 2012 ), XPREP (Bruker, 2012) and WinGX (Farrugia, 2012).

2.5. The Cambridge Structural Database (CSD)

The CSD (Version 2022.1.0; Groom et al., 2016) was used to compare the cocrystals presented in this work with the cocrystals of izact. The only restriction was that entries must be classified as being organic. Mercury (Macrae et al., 2020 ) was used to inspect the crystal structures. The Crystal Structure Similarity tool was used to compare the structural similarity of selected structures.

2.6. Differential scanning calorimetry (DSC)

DSC data were collected using a Mettler Toledo DSC 3 with aluminium pans under nitrogen gas (flow rate = 10 ml min⁻¹). Exothermic events were shown as peaks. Samples were heated and cooled to determine the melting points, as well as any additional phase transitions. The temperature and energy calibrations were performed using pure indium (purity 99.99%, m.p. 156.6 °C, heat of fusion: 28.45 J g⁻¹) and pure zinc (purity 99.99%, m.p. 479.5 °C, heat of fusion: 107.5 J g⁻¹). Samples were heated to 250 °C from 25 °C before being cooled back down to 25 °C at a heating or cooling rate of 10 °C min⁻¹.

3. Results and discussion

3.1. Synthesis of cocrystals

In this work, six cocrystals were synthesized and characterized. Five of these cocrystals contained izbt and one contained izact. The four coformers chosen were: 2,4-dihydroxybenzoic acid (2,4-dhba), 2,5-dihydroxybenzoic acid (gentisic acid, abbreviated as 2,5-dhba), 2-chloro-4-nitrobenzoic acid (2c4n) and 1-naphthoic acid (1nta). The first three coformers were chosen because previous cocrystals containing said coformers with izact had been synthesized and characterized previously, and it would be a good reference to compare the respective corystals. 1nta was chosen due to its naphthalene ring, as it would be interesting to see if its bulky nature had an effect on the overall packing. These cocrystals are described below, together with that of izbt compared to its izact counterpart, as well as any other notable cocrystal of izact. The crystal structure data are given in Table 2, while the displacement ellipsoid plots are shown in Fig. 1. Hydrogen-bond tables can be found in the supporting information.

Figure 1
The molecular structures of (a) izbt–2c4n, (b) izact–1nta, (c) izbt–2,4-dhba, (d) izbt–1nta and (e) izbt–2,5-dhba. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Powder patterns were collected for each sample and were compared to the powder patterns calculated from the single-crystal structural data. These powder patterns are also compared to the powder patterns of each of the components, including the polymorphic forms of the components which are polymorphic. It should be noted that we are comparing the hydrated form of izbt to the powder patterns of the cocrystals presented here. This was done because it was the closest form to a `pure' component we can get, and in our own investigations, we have obtained the hydrated form of izbt exclusively when using the same crystallizing conditions we used to obtain the cocrystals presented here, which indicates that izbt is most likely highly hygroscopic, obtaining the water from either the waters of reaction or atmospheric moisture, or both. This comparison between the experimental and calculated patterns was made to confirm the bulk phase purity. These patterns are presented in the supporting information.

3.2. Crystal structure of izbt–2,4-dhba

Izbt formed a cocrystal with 2,4-dhba which crystallized as colourless blocks in the space group P2₁/n, with the asymmetric unit consisting of one molecule each of izbt and 2,4-dhba. A disorder model is present, where two C atoms (C9 and C10) of the alkyl portion of izbt were split over two different positions, respectively. The pyridine ring of izbt forms a hydrogen bond with the carboxylic acid group of 2,4-dhba, while the hydroxy group at the 4-position of the 2,4-dhba molecule (O5—H5) forms two different hydrogen bonds with the amide group of izbt, one where the hydroxy group is the hydrogen-bond donor, forming a hydrogen bond with the O atom of the amide group [O5—H5⋯O1ⁱ; symmetry code: (i) x + $[{3\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ], and one where the hydroxy group is the hydrogen-bond acceptor, forming a hydrogen bond with the amine portion of the amide group [N1—H1⋯O5ⁱⁱ; symmetry code: (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ] [Fig. 2(a)]. This hydrogen-bond arrangement ultimately forms a tetramer with an R₄⁴(12) ring hydrogen-bond motif. The hydroxy group at the 2-position of 2,4-dhba does not form any strong hydrogen bonds other than the typical intramolecular hydrogen bond with the carboxylic acid group. The overall packing of the structure resembles a herringbone-type structure [Fig. 2(b)].

Figure 2
The crystal structure of izbt–2,4-dhba, showing (a) the hydrogen bonding present in the structure, (b) the packing of the structure (with H atoms omitted) and (c) an overlay of izbt–2,4-dhba with izact–4hba, showing their isostructurality.

Although there is no equivalent cocrystal featuring 2,4-dhba and izact, the crystal structure of izbt–2,4-dhba may be compared to that of izact–4hba (CSD refcode LATKOI). Fig. 2(c) shows the overlay of these two structures using the Crystal Structure Similarity tool of Mercury (Macrae et al., 2020). The crystal structure parameters of izact–4hba match closely with those of izbt–2,4-dhba, and when the Crystal Structure Similarity tool of Mercury was used, it showed that the respective molecules matched up well, indicating that they were isostructural. This implies that, in this case, the hydroxy group at the 2-position and the extra methyl group on the alkyl chain did not have any significant effect on the overall packing on the structure.

3.3. Crystal structure of izbt–2,5-dhba

Izbt formed a cocrystal with 2,5-dhba which crystallized as colourless blocks in the space group P $[\overline 1]$ , with the asymmetric unit consisting of two molecules each of izbt and 2,5-dhba. A disorder model exists where the methylene group of one of the izbt molecules has been split into two different sites (C26A and C26B). Like izbt–2,4-dhba, the corystals of izbt–2,5-dhba exhibit a similar hydrogen-bonding trend: a hydrogen bond is formed between the pyridine ring of izbt and the carboxylic acid group of 2,5-dhba, while the hydroxy group at the 5-position of 2,5-dhba forms a C₂²(11) chain–ring hydrogen-bond motif with the O and H atom of the amide group of adjacent izbt molecules [Fig. 3(a)]. The overall packing is a layered-type structure, with the alkyl group separating the ring layers [Fig. 3(b)]. In comparison, the structure of izact–2,5-dhba (refcode NAKYOQ; Oruganti et al., 2016 ) is very similar to its izbt counterpart. Both exhibit the same hydrogen-bond pattern, as well as the overall packing pattern, and the reduced unit-cell lengths of NAKYOQ are comparable (a = 9.119, b = 11.581 and c = 15.273 Å) [Fig. 3(c)].

Figure 3
The crystal structure of izbt–2,5-dhba, showing (a) the hydrogen bonding present, (b) the packing (with H atoms omitted, izbt in blue and green, and 2,5-dhba in red and yellow) and (c) the overlay of izact–2,5-dhba and izbt–2,5-dhba.

3.4. Crystal structure of izbt–2c4n

Izbt and 2c4n formed a cocrystal, crystallizing as yellow plates. The asymmetric unit consists of one molecule each of izbt and 2c4n, crystallizing in the space group P2₁/n. The hydrogen bonding observed in izact–2c4n consists of the typical scheme observed for these types of structures: the carboxylic acid group of 2c4n forms a hydrogen bond with the pyridine ring of izbt, while the amide group of izbt forms a C(4) chain hydrogen-bond motif between the H atom of the amide group and the O atom of the amide group of another izbt molecule [Fig. 4(a)]. This chain hydrogen-bond motif causes the molecules of izbt to lie almost perpendicular with respect to each other in an alternating pattern, and extends along the a and c axes. This ultimately forms a series of ribbons which pack together to form the crystal structure observed in Fig. 4(c).

Figure 4
The crystal structure of izbt–2c4n and izact–2c4n (CSD refcode LATLID), showing (a) the hydrogen bonding present in izbt–2c4n, (b) the asymmetric unit of izact–2c4n, (c) the packing of izbt–2c4n (with H atoms omitted for clarity) and (d) the packing of izact–2c4n (with H atoms omitted for clarity).

The izact–2c4n cocrystal (refcode LATLID) is much different in comparison. According to Grothe et al. (2016), this crystal system can be defined as a `cocrystal salt', since its asymmetric unit consists of three neutral molecules of 2c4n and one ion of 2c4n, with three neutral molecules of izact and one protonated ion of izact [Fig. 4(b)]. This crystal structure crystallizes in the chiral space group P2₁. Like the structure of izbt–2c4n, molecules and ions of izact are connected to each other via a series of C₄⁴(16) chain hydrogen-bond motifs involving the H atom of the amide group forming a hydrogen bond with the O atom of the amide group from another izact molecule. The carboxylic acid group of 2c4n also forms a hydrogen bond with the pyridine ring of izact (charge-assisted for the cation–anion pair). The overall packing of izact–2c4n also consists of ribbons, but these differ from the structure of izbt–2c4n [Fig. 4(d)]. Unlike in the crystal structure of izbt–2c4n, the arrangement of the izbt–2c4n bonded pairs lie almost parallel to each other, instead of the rotation of almost 90° seen in izbt–2c4n.

3.5. Crystal structures of izact–1nta and izbt–1nta

Izact and izbt each formed a cocrystal with 1nta, both crystallizing as colourless plates. Despite sharing similar unit-cell parameters, the structures are not isostructural, as the crystal structure of izact–1nta crystallizes in the space group Cc, while the crystal structure of izbt–1nta crystallizes in the space group P2₁/n. These structures are also not isostructural with izbt–2c4n, despite sharing similar unit-cell parameters, as can be seen in Fig. 5(d). Both crystal structures share the same hydrogen-bonding patterns. 1nta forms a hydrogen bond with the isoniazid derivative, while the isoniazid derivative forms a C(4) chain hydrogen-bond motif involving the H atom of the amide group and the O atom of the amide group from a neighbouring molecule of the isoniazid derivative [Fig. 5(a)], which expands generally in the direction of the a axis as ribbons. The key difference between the two structures lies in the packing, where the difference between the P2₁/n and Cc space groups is that the inversion centres in P2₁/n [Fig. 5(b)] are replaced by glide planes in Cc [Fig. 5(c)]. This changes the orientation of the molecules existing in both structures with respect to the unit cell. Overall, the packing of both structures may be described as herringbone.

Figure 5
(a) The hydrogen bonding present in izact–1nta, showing the typical hydrogen bonding in the structures of izact–1nta and izbt–1nta. The packing present in the crystal structure of (b) izact–1nta and (c) izbt–1nta, with the H atoms omitted for clarity. In parts (b) and (c), the respective isoniazid derivative is presented in green, 1nta in blue, glide planes as magenta lines and inversion centres as orange spheres. (d) The overlap of izbt–1nta and izbt–2c4n (molecules in green), showing that the structures are not isostructural.

3.6. Thermal analysis

DSC curves were collected for all ten cocrystals. The DSC curve of izbt–1nta is presented in Fig. 6 as a representative curve, while the remaining DSC curves can be found in the supporting information. The onset and enthalpy values are presented in Table 3. The melting points and enthalpies of some of the cocrystals related to the cocrystals presented in this work are also included. In each of the curves, only one large distinct peak was observed on the heating stage, which correlates to the melting/decomposition of the sample. No peaks were observed on the cooling stage of the DSC curves, indicating that no recrystallization occurred. A common feature between the cocrystals is that their melting points are much lower than the melting points of the acid coformers. This makes sense since the R₂²(8) hydrogen-bond ring motif formed between the carboxylic acid pairs is expected to be stronger than that formed by carboxylic acid–pyridine. From a pharmaceutical point of view, a lower melting point is usually indicative of a product that has a better drug solubility, which indicates the possibility of having better pharmaceutical properties compared to their individual components (Chu & Yalkowsky, 2009 ). A comparison of the melting/decomposition points and enthalpies of the izact cocrystals with those of their izbt counterparts indicates that the values tend to be similar to each other, which would make sense considering their overall similar hydrogen-bond schemes.

Table 3
Onset temperatures and associated enthalpies for the DSC curves of the cocrystals presented in this work, as well as the melting points and enthalpies of some of the comparison cocrystals

Thermal event	Onset (°C)	Enthalpy (J g⁻¹)	Enthalpy (kJ mol⁻¹)
Izact–1nta melting/decomposition	106.1 ± 0.5	170.9 ± 5.2	59.7 ± 2
Izbt–1nta melting/decomposition	89.5± 0.1	167.8 ± 2.5	61.0 ± 1
Izbt–2c4n melting/decomposition	102.1 ± 0.2	100.6 ± 2.3	39.5 ± 1
Izbt–2,4-dhba melting/decomposition	174.8± 0.2	226.3 ± 4.3	78.2 ± 1
Izbt–2,5-dhba melting/decomposition	151.2 ± 0.2	132.5 ± 3.2	45.8 ± 1
Izact m.p. (Lemmerer, 2012)	160.0	–	29.7
Izact–2c4n m.p. (Lemmerer, 2012)	93.4	–	33.4

Figure 6
DSC curve for izbt–1nta, representing the typical DSC curve observed for each of the cocrystals.

4. Conclusions

Four cocrystals containing izbt and one cocrystal containing izact were synthesized and characterized. The structures of the cocrystals containing izbt were compared to their izact counterparts, except for izbt–2,4-dhba, which was instead compared to izact–4hba. Most of the structures of the cocrystals of izbt were different compared to their izact counterparts in terms of packing, despite sharing similar hydrogen-bond patterns. This would imply that the presence or absence of a methylene group can have a significant impact on the overall crystal structure packing, contrary to our initial assumption that the methylene group has a small or even insignificant effect on the packing of molecules in the crystal structure. The melting/decomposition points were found to be much lower than those of the coformers. The overall result shows that many crystal systems are temperamental: small differences between molecules can lead to big changes in the overall packing.

Supporting information

CCDC references: 2264437; 2264438; 2264434; 2264436; 2264435

Crystal structure: contains datablocks izbt1nta, izbt24dhba, izact1nta, izbt2c4n, izbt25dhba, global. DOI: https://doi.org/10.1107/S2053229623007179/dv3024sup1.cif

Structure factors: contains datablock izbt1nta. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt1ntasup2.hkl

Structure factors: contains datablock izbt24dhba. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt24dhbasup3.hkl

Structure factors: contains datablock izact1nta. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izact1ntasup4.hkl

Structure factors: contains datablock izbt2c4n. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt2c4nsup5.hkl

Structure factors: contains datablock izbt25dhba. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt25dhbasup6.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt1ntasup7.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt24dhbasup8.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izact1ntasup9.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt2c4nsup10.cml

Supporting information file. DOI: https://doi.org/10.1107/S2053229623007179/dv3024izbt25dhbasup11.cml

Additional tables and figures. DOI: https://doi.org/10.1107/S2053229623007179/dv3024sup12.pdf

Computing details top

Data collection: APEX2 (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. Cell refinement: SAINT-Plus (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. Data reduction: SAINT-Plus (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n. For all structures, program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n; ORTEP-3 for Windows (Farrugia, 2012) for izbt25dhba. Software used to prepare material for publication: WinGX (Farrugia, 2012) and XPREP (Bruker, 2012) for izbt1nta, izbt24dhba, izact1nta, izbt2c4n; WinGX (Farrugia, 2012) for izbt25dhba.

N'-(Butan-2-ylidene)pyridine-4-carbohydrazide; 1-naphthoic acid (izbt1nta) top

Crystal data top

C₁₀H₁₃N₃O·C₁₁H₈O₂	F(000) = 768
M_r = 363.41	D_x = 1.33 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9890 reflections
a = 7.4355 (13) Å	θ = 2.9–28.3°
b = 34.195 (6) Å	µ = 0.09 mm⁻¹
c = 7.7242 (14) Å	T = 173 K
β = 112.512 (4)°	Block, colourless
V = 1814.3 (6) Å³	0.34 × 0.28 × 0.12 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.033
φ and ω scans	θ_max = 28.3°, θ_min = 3.4°
35501 measured reflections	h = −9→9
4511 independent reflections	k = −45→45
3552 reflections with I > 2σ(I)	l = −10→10

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0637P)² + 1.0375P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4511 reflections	Δρ_max = 0.54 e Å⁻³
254 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4865 (3)	0.64234 (5)	0.5961 (2)	0.0289 (4)
H1	0.479346	0.614625	0.599541	0.035*
C2	0.5137 (2)	0.66303 (4)	0.7582 (2)	0.0244 (3)
H2A	0.528577	0.649764	0.870961	0.029*
C3	0.5189 (2)	0.70353 (4)	0.7527 (2)	0.0208 (3)
C4	0.5009 (2)	0.72157 (5)	0.5857 (2)	0.0264 (3)
H4	0.504198	0.749257	0.577421	0.032*
C5	0.4780 (3)	0.69843 (5)	0.4313 (2)	0.0300 (4)
H5	0.467633	0.710899	0.317944	0.036*
C6	0.5592 (2)	0.72591 (4)	0.9309 (2)	0.0219 (3)
C7	0.4945 (2)	0.82004 (5)	1.0579 (2)	0.0269 (3)
C8	0.4585 (3)	0.84331 (5)	0.8828 (2)	0.0367 (4)
H8A	0.514858	0.829582	0.804171	0.055*
H8B	0.519033	0.86913	0.916433	0.055*
H8C	0.317967	0.846392	0.813647	0.055*
C9	0.5210 (3)	0.84343 (5)	1.2308 (2)	0.0312 (4)
H9A	0.630337	0.861863	1.253523	0.037*
H9B	0.402059	0.859191	1.20623	0.037*
C10	0.5606 (3)	0.82005 (6)	1.4061 (2)	0.0376 (4)
H10A	0.448383	0.803278	1.389922	0.056*
H10B	0.582875	0.837824	1.511822	0.056*
H10C	0.676282	0.80377	1.430932	0.056*
C11	0.3204 (2)	0.54602 (4)	0.0208 (2)	0.0218 (3)
C12	0.3179 (2)	0.55966 (4)	−0.1480 (2)	0.0241 (3)
H12	0.354523	0.585992	−0.156468	0.029*
C13	0.2629 (2)	0.53579 (5)	−0.3079 (2)	0.0281 (3)
H13	0.26264	0.545884	−0.42259	0.034*
C14	0.2099 (2)	0.49802 (5)	−0.2971 (2)	0.0289 (4)
H14	0.172404	0.481852	−0.405159	0.035*
C15	0.2097 (2)	0.48253 (5)	−0.1277 (2)	0.0253 (3)
C16	0.2665 (2)	0.50632 (4)	0.0363 (2)	0.0221 (3)
C17	0.2661 (2)	0.48883 (5)	0.2031 (2)	0.0282 (3)
H17	0.304248	0.503862	0.314877	0.034*
C18	0.2117 (3)	0.45067 (5)	0.2051 (3)	0.0346 (4)
H18	0.212744	0.439598	0.318294	0.042*
C19	0.1544 (3)	0.42767 (5)	0.0429 (3)	0.0374 (4)
H19	0.116051	0.401269	0.046069	0.045*
C20	0.1539 (3)	0.44330 (5)	−0.1191 (3)	0.0334 (4)
H20	0.115288	0.427542	−0.22866	0.04*
C21	0.3808 (2)	0.57384 (5)	0.1818 (2)	0.0273 (3)
N1	0.4697 (2)	0.65943 (4)	0.43437 (19)	0.0295 (3)
N2	0.4799 (2)	0.76157 (4)	0.91231 (18)	0.0261 (3)
N3	0.5099 (2)	0.78278 (4)	1.07692 (18)	0.0273 (3)
O1	0.66638 (17)	0.71153 (3)	1.08121 (15)	0.0301 (3)
O2	0.3999 (2)	0.61035 (4)	0.13403 (18)	0.0412 (3)
O3	0.4134 (3)	0.56528 (4)	0.34138 (18)	0.0645 (5)
H2	0.385 (3)	0.7684 (6)	0.805 (3)	0.039 (5)*
H2B	0.432 (4)	0.6256 (8)	0.232 (4)	0.063 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0369 (9)	0.0208 (8)	0.0284 (8)	−0.0006 (6)	0.0117 (7)	−0.0033 (6)
C2	0.0285 (8)	0.0207 (7)	0.0221 (7)	−0.0009 (6)	0.0077 (6)	−0.0003 (6)
C3	0.0202 (7)	0.0208 (7)	0.0193 (7)	0.0001 (5)	0.0051 (5)	−0.0027 (5)
C4	0.0349 (9)	0.0202 (7)	0.0246 (7)	0.0004 (6)	0.0119 (6)	0.0001 (6)
C5	0.0404 (9)	0.0287 (8)	0.0232 (7)	−0.0007 (7)	0.0148 (7)	−0.0006 (6)
C6	0.0232 (7)	0.0210 (7)	0.0199 (7)	−0.0030 (6)	0.0064 (6)	−0.0028 (5)
C7	0.0236 (8)	0.0261 (8)	0.0295 (8)	−0.0014 (6)	0.0085 (6)	−0.0070 (6)
C8	0.0486 (11)	0.0262 (9)	0.0314 (9)	−0.0017 (7)	0.0113 (8)	−0.0017 (7)
C9	0.0349 (9)	0.0269 (8)	0.0332 (9)	−0.0017 (7)	0.0145 (7)	−0.0080 (7)
C10	0.0428 (10)	0.0366 (10)	0.0337 (9)	−0.0006 (8)	0.0150 (8)	−0.0074 (7)
C11	0.0234 (7)	0.0218 (7)	0.0201 (7)	0.0016 (6)	0.0083 (6)	−0.0012 (5)
C12	0.0283 (8)	0.0216 (7)	0.0230 (7)	0.0012 (6)	0.0103 (6)	0.0006 (6)
C13	0.0335 (9)	0.0307 (8)	0.0205 (7)	0.0028 (7)	0.0106 (6)	0.0001 (6)
C14	0.0295 (8)	0.0321 (8)	0.0224 (7)	0.0021 (7)	0.0069 (6)	−0.0077 (6)
C15	0.0219 (7)	0.0239 (7)	0.0285 (8)	0.0016 (6)	0.0081 (6)	−0.0028 (6)
C16	0.0209 (7)	0.0216 (7)	0.0241 (7)	0.0033 (6)	0.0090 (6)	0.0007 (6)
C17	0.0320 (9)	0.0267 (8)	0.0294 (8)	0.0029 (6)	0.0156 (7)	0.0021 (6)
C18	0.0378 (10)	0.0298 (9)	0.0424 (10)	0.0037 (7)	0.0224 (8)	0.0095 (7)
C19	0.0381 (10)	0.0232 (8)	0.0527 (11)	−0.0032 (7)	0.0195 (9)	0.0022 (8)
C20	0.0318 (9)	0.0254 (8)	0.0408 (10)	−0.0019 (7)	0.0114 (7)	−0.0065 (7)
C21	0.0344 (9)	0.0241 (8)	0.0229 (7)	−0.0005 (6)	0.0105 (6)	−0.0019 (6)
N1	0.0368 (8)	0.0279 (7)	0.0250 (7)	−0.0007 (6)	0.0130 (6)	−0.0058 (5)
N2	0.0306 (7)	0.0231 (7)	0.0194 (6)	0.0020 (5)	0.0037 (5)	−0.0051 (5)
N3	0.0294 (7)	0.0270 (7)	0.0231 (6)	−0.0010 (5)	0.0075 (5)	−0.0077 (5)
O1	0.0364 (6)	0.0266 (6)	0.0193 (5)	0.0020 (5)	0.0017 (5)	−0.0001 (4)
O2	0.0758 (10)	0.0223 (6)	0.0276 (6)	−0.0044 (6)	0.0222 (7)	−0.0052 (5)
O3	0.1335 (16)	0.0346 (8)	0.0231 (7)	−0.0192 (9)	0.0272 (8)	−0.0066 (5)

Geometric parameters (Å, º) top

C1—N1	1.341 (2)	C11—C12	1.378 (2)
C1—C2	1.384 (2)	C11—C16	1.433 (2)
C1—H1	0.95	C11—C21	1.492 (2)
C2—C3	1.387 (2)	C12—C13	1.404 (2)
C2—H2A	0.95	C12—H12	0.95
C3—C4	1.389 (2)	C13—C14	1.362 (2)
C3—C6	1.5016 (19)	C13—H13	0.95
C4—C5	1.386 (2)	C14—C15	1.412 (2)
C4—H4	0.95	C14—H14	0.95
C5—N1	1.335 (2)	C15—C20	1.413 (2)
C5—H5	0.95	C15—C16	1.427 (2)
C6—O1	1.2311 (18)	C16—C17	1.422 (2)
C6—N2	1.338 (2)	C17—C18	1.368 (2)
C7—N3	1.283 (2)	C17—H17	0.95
C7—C8	1.502 (2)	C18—C19	1.400 (3)
C7—C9	1.504 (2)	C18—H18	0.95
C8—H8A	0.98	C19—C20	1.359 (3)
C8—H8B	0.98	C19—H19	0.95
C8—H8C	0.98	C20—H20	0.95
C9—C10	1.501 (2)	C21—O3	1.198 (2)
C9—H9A	0.99	C21—O2	1.325 (2)
C9—H9B	0.99	N2—N3	1.4054 (17)
C10—H10A	0.98	N2—H2	0.89 (2)
C10—H10B	0.98	O2—H2B	0.87 (3)
C10—H10C	0.98

N1—C1—C2	123.30 (15)	C12—C11—C16	119.79 (13)
N1—C1—H1	118.3	C12—C11—C21	117.61 (14)
C2—C1—H1	118.3	C16—C11—C21	122.60 (13)
C1—C2—C3	118.61 (14)	C11—C12—C13	121.94 (14)
C1—C2—H2A	120.7	C11—C12—H12	119
C3—C2—H2A	120.7	C13—C12—H12	119
C2—C3—C4	118.55 (13)	C14—C13—C12	119.39 (14)
C2—C3—C6	118.61 (13)	C14—C13—H13	120.3
C4—C3—C6	122.66 (13)	C12—C13—H13	120.3
C5—C4—C3	118.82 (14)	C13—C14—C15	121.05 (14)
C5—C4—H4	120.6	C13—C14—H14	119.5
C3—C4—H4	120.6	C15—C14—H14	119.5
N1—C5—C4	123.08 (15)	C14—C15—C20	120.28 (15)
N1—C5—H5	118.5	C14—C15—C16	120.26 (14)
C4—C5—H5	118.5	C20—C15—C16	119.46 (15)
O1—C6—N2	124.39 (14)	C17—C16—C15	117.54 (14)
O1—C6—C3	119.40 (13)	C17—C16—C11	124.88 (14)
N2—C6—C3	116.15 (12)	C15—C16—C11	117.57 (13)
N3—C7—C8	127.34 (14)	C18—C17—C16	120.98 (15)
N3—C7—C9	116.82 (15)	C18—C17—H17	119.5
C8—C7—C9	115.82 (14)	C16—C17—H17	119.5
C7—C8—H8A	109.5	C17—C18—C19	121.03 (16)
C7—C8—H8B	109.5	C17—C18—H18	119.5
H8A—C8—H8B	109.5	C19—C18—H18	119.5
C7—C8—H8C	109.5	C20—C19—C18	119.72 (16)
H8A—C8—H8C	109.5	C20—C19—H19	120.1
H8B—C8—H8C	109.5	C18—C19—H19	120.1
C10—C9—C7	115.56 (14)	C19—C20—C15	121.26 (16)
C10—C9—H9A	108.4	C19—C20—H20	119.4
C7—C9—H9A	108.4	C15—C20—H20	119.4
C10—C9—H9B	108.4	O3—C21—O2	121.05 (15)
C7—C9—H9B	108.4	O3—C21—C11	125.43 (15)
H9A—C9—H9B	107.5	O2—C21—C11	113.50 (13)
C9—C10—H10A	109.5	C5—N1—C1	117.61 (14)
C9—C10—H10B	109.5	C6—N2—N3	117.53 (12)
H10A—C10—H10B	109.5	C6—N2—H2	119.9 (13)
C9—C10—H10C	109.5	N3—N2—H2	120.1 (14)
H10A—C10—H10C	109.5	C7—N3—N2	115.64 (13)
H10B—C10—H10C	109.5	C21—O2—H2B	110.2 (17)

N1—C1—C2—C3	1.8 (3)	C12—C11—C16—C17	179.06 (15)
C1—C2—C3—C4	−1.4 (2)	C21—C11—C16—C17	−0.8 (2)
C1—C2—C3—C6	−176.73 (14)	C12—C11—C16—C15	−0.7 (2)
C2—C3—C4—C5	0.2 (2)	C21—C11—C16—C15	179.46 (14)
C6—C3—C4—C5	175.28 (15)	C15—C16—C17—C18	−0.5 (2)
C3—C4—C5—N1	0.9 (3)	C11—C16—C17—C18	179.73 (16)
C2—C3—C6—O1	32.2 (2)	C16—C17—C18—C19	−0.1 (3)
C4—C3—C6—O1	−142.93 (16)	C17—C18—C19—C20	0.4 (3)
C2—C3—C6—N2	−150.56 (15)	C18—C19—C20—C15	−0.2 (3)
C4—C3—C6—N2	34.3 (2)	C14—C15—C20—C19	179.39 (16)
N3—C7—C9—C10	−0.6 (2)	C16—C15—C20—C19	−0.4 (2)
C8—C7—C9—C10	−178.93 (16)	C12—C11—C21—O3	−170.22 (19)
C16—C11—C12—C13	0.3 (2)	C16—C11—C21—O3	9.6 (3)
C21—C11—C12—C13	−179.86 (14)	C12—C11—C21—O2	8.6 (2)
C11—C12—C13—C14	0.1 (2)	C16—C11—C21—O2	−171.56 (15)
C12—C13—C14—C15	−0.1 (2)	C4—C5—N1—C1	−0.7 (3)
C13—C14—C15—C20	179.88 (16)	C2—C1—N1—C5	−0.7 (3)
C13—C14—C15—C16	−0.3 (2)	O1—C6—N2—N3	−4.8 (2)
C14—C15—C16—C17	−179.06 (14)	C3—C6—N2—N3	178.06 (13)
C20—C15—C16—C17	0.7 (2)	C8—C7—N3—N2	−3.4 (2)
C14—C15—C16—C11	0.7 (2)	C9—C7—N3—N2	178.55 (14)
C20—C15—C16—C11	−179.47 (14)	C6—N2—N3—C7	156.63 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3	0.95	2.51	3.208 (2)	130
C8—H8C···O1ⁱ	0.98	2.62	3.128 (2)	112
N2—H2···O1ⁱ	0.89 (2)	1.98 (2)	2.8732 (17)	174 (2)
O2—H2B···N1	0.87 (3)	1.88 (3)	2.7472 (18)	173 (2)

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.

N'-(Butan-2-ylidene)pyridine-4-carbohydrazide; 2,4-dihydroxybenzoic acid (izbt24dhba) top

Crystal data top

C₁₀H₁₃N₃O·C₇H₆O₄	F(000) = 728
M_r = 345.35	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2614 reflections
a = 11.0834 (6) Å	θ = 2.4–21.7°
b = 13.8364 (8) Å	µ = 0.10 mm⁻¹
c = 12.0014 (7) Å	T = 173 K
β = 115.710 (3)°	Block, colourless
V = 1658.26 (17) Å³	0.32 × 0.25 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.092
φ and ω scans	θ_max = 28.0°, θ_min = 2.1°
25708 measured reflections	h = −14→14
4008 independent reflections	k = −14→18
1946 reflections with I > 2σ(I)	l = −15→15

Refinement top

Refinement on F²	0 constraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.219	w = 1/[σ²(F_o²) + (0.1075P)² + 0.2167P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4008 reflections	Δρ_max = 0.70 e Å⁻³
248 parameters	Δρ_min = −0.27 e Å⁻³
39 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2256 (3)	0.3307 (2)	0.1115 (2)	0.0462 (7)
C2	0.3201 (3)	0.3638 (2)	0.2233 (3)	0.0517 (7)
H2A	0.294648	0.40267	0.274882	0.062*
C3	0.4529 (3)	0.3395 (2)	0.2596 (3)	0.0565 (8)
H3	0.517455	0.363307	0.336671	0.068*
C4	0.4034 (3)	0.2515 (3)	0.0874 (3)	0.0656 (9)
H4A	0.431538	0.211008	0.039242	0.079*
C5	0.2688 (3)	0.2722 (2)	0.0432 (3)	0.0611 (8)
H5A	0.20651	0.246347	−0.033661	0.073*
C6	0.0790 (3)	0.3539 (2)	0.0579 (3)	0.0486 (7)
C7	−0.0363 (4)	0.4971 (3)	0.2909 (4)	0.0926 (13)
H7A	−0.085959	0.531016	0.329609	0.139*
H7B	−0.00322	0.435334	0.333219	0.139*
H7C	0.03954	0.536836	0.297237	0.139*
C8	−0.1270 (3)	0.4788 (2)	0.1576 (4)	0.0669 (9)
C9A	−0.2718 (8)	0.5139 (7)	0.0969 (7)	0.068 (2)	0.681 (9)
H9A1	−0.273761	0.584595	0.109021	0.082*	0.681 (9)
H9A2	−0.310308	0.501278	0.006909	0.082*	0.681 (9)
C10A	−0.3526 (6)	0.4664 (5)	0.1481 (7)	0.093 (2)	0.681 (9)
H10A	−0.444645	0.490666	0.107151	0.14*	0.681 (9)
H10B	−0.352183	0.396541	0.134913	0.14*	0.681 (9)
H10C	−0.315658	0.479809	0.236963	0.14*	0.681 (9)
C9B	−0.2550 (16)	0.5059 (17)	0.1534 (14)	0.086 (5)	0.319 (9)
H9B1	−0.266817	0.476516	0.223158	0.104*	0.319 (9)
H9B2	−0.261527	0.577059	0.158046	0.104*	0.319 (9)
C10B	−0.3542 (15)	0.4705 (11)	0.0377 (13)	0.095 (4)	0.319 (9)
H10D	−0.443548	0.486929	0.029738	0.143*	0.319 (9)
H10E	−0.340753	0.500108	−0.030243	0.143*	0.319 (9)
H10F	−0.346015	0.400111	0.034516	0.143*	0.319 (9)
N1	0.0399 (2)	0.40980 (18)	0.1262 (2)	0.0549 (7)
H1	0.098313	0.429903	0.199395	0.066*
N2	0.4951 (2)	0.28521 (19)	0.1933 (2)	0.0582 (7)
N3	−0.0929 (2)	0.43602 (19)	0.0816 (3)	0.0626 (7)
O1	0.00257 (19)	0.32187 (16)	−0.0423 (2)	0.0651 (6)
C11	0.9062 (2)	0.17767 (19)	0.1967 (2)	0.0437 (6)
C12	0.9337 (3)	0.1210 (2)	0.1135 (3)	0.0462 (7)
C13	1.0644 (3)	0.0963 (2)	0.1403 (3)	0.0483 (7)
H13	1.082847	0.058264	0.083628	0.058*
C14	1.1674 (2)	0.1266 (2)	0.2486 (3)	0.0461 (7)
C15	1.1424 (3)	0.1830 (2)	0.3328 (3)	0.0518 (7)
H15	1.213819	0.20393	0.407784	0.062*
C16	1.0126 (3)	0.2074 (2)	0.3052 (3)	0.0497 (7)
H16	0.994989	0.245932	0.362002	0.06*
C17	0.7666 (3)	0.2014 (2)	0.1685 (3)	0.0473 (7)
O2	0.74959 (18)	0.25109 (16)	0.25335 (18)	0.0598 (6)
H2	0.667349	0.259116	0.231809	0.09*
O3	0.67159 (18)	0.17496 (15)	0.07253 (18)	0.0559 (6)
O4	0.83565 (18)	0.08837 (17)	0.00710 (18)	0.0614 (6)
H4	0.760984	0.105658	0.002523	0.092*
O5	1.29304 (18)	0.09825 (15)	0.27164 (19)	0.0567 (6)
H5	1.348308	0.124958	0.336623	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0322 (13)	0.0605 (18)	0.0483 (17)	0.0021 (12)	0.0197 (13)	0.0023 (13)
C2	0.0377 (15)	0.069 (2)	0.0518 (18)	0.0077 (13)	0.0226 (14)	0.0001 (15)
C3	0.0337 (14)	0.078 (2)	0.0557 (18)	0.0036 (14)	0.0172 (14)	−0.0056 (16)
C4	0.0418 (16)	0.097 (3)	0.066 (2)	0.0071 (16)	0.0309 (17)	−0.0140 (18)
C5	0.0379 (15)	0.088 (2)	0.0595 (19)	0.0001 (15)	0.0230 (15)	−0.0129 (17)
C6	0.0323 (14)	0.0587 (18)	0.0574 (19)	0.0000 (12)	0.0218 (15)	0.0013 (14)
C7	0.080 (3)	0.106 (3)	0.125 (4)	−0.013 (2)	0.076 (3)	−0.028 (3)
C8	0.0505 (18)	0.064 (2)	0.105 (3)	0.0021 (15)	0.050 (2)	0.0004 (19)
C9A	0.056 (4)	0.088 (4)	0.071 (5)	0.016 (3)	0.037 (4)	0.006 (4)
C10A	0.064 (4)	0.103 (5)	0.135 (6)	0.010 (3)	0.064 (4)	0.018 (4)
C9B	0.063 (8)	0.110 (10)	0.113 (11)	0.027 (7)	0.063 (8)	0.018 (10)
C10B	0.098 (9)	0.086 (9)	0.132 (10)	0.009 (7)	0.079 (8)	−0.007 (8)
N1	0.0325 (12)	0.0766 (17)	0.0606 (16)	0.0031 (11)	0.0250 (12)	−0.0011 (13)
N2	0.0351 (12)	0.0826 (19)	0.0602 (16)	0.0074 (12)	0.0237 (13)	−0.0070 (14)
N3	0.0336 (12)	0.0738 (18)	0.0819 (19)	0.0088 (11)	0.0265 (13)	0.0040 (14)
O1	0.0379 (11)	0.0789 (15)	0.0678 (15)	0.0051 (10)	0.0129 (11)	−0.0127 (12)
C11	0.0340 (13)	0.0511 (17)	0.0505 (16)	0.0028 (11)	0.0226 (13)	0.0028 (13)
C12	0.0325 (13)	0.0589 (18)	0.0467 (17)	−0.0021 (12)	0.0168 (13)	−0.0012 (13)
C13	0.0383 (14)	0.0592 (18)	0.0535 (17)	0.0019 (12)	0.0257 (14)	−0.0057 (14)
C14	0.0311 (13)	0.0525 (17)	0.0561 (18)	0.0036 (11)	0.0201 (14)	−0.0002 (13)
C15	0.0346 (14)	0.0643 (19)	0.0531 (18)	−0.0004 (12)	0.0158 (13)	−0.0096 (14)
C16	0.0364 (14)	0.0598 (18)	0.0549 (18)	0.0042 (12)	0.0216 (14)	−0.0067 (14)
C17	0.0352 (14)	0.0590 (18)	0.0507 (17)	0.0041 (12)	0.0215 (14)	0.0058 (14)
O2	0.0373 (10)	0.0837 (15)	0.0614 (13)	0.0108 (10)	0.0242 (10)	−0.0097 (11)
O3	0.0325 (10)	0.0817 (15)	0.0535 (13)	0.0023 (9)	0.0187 (10)	−0.0035 (10)
O4	0.0361 (10)	0.0921 (16)	0.0542 (13)	0.0026 (10)	0.0179 (10)	−0.0153 (11)
O5	0.0316 (10)	0.0738 (14)	0.0651 (14)	0.0044 (9)	0.0212 (10)	−0.0110 (10)

Geometric parameters (Å, º) top

C1—C2	1.374 (4)	C9B—C10B	1.432 (10)
C1—C5	1.378 (4)	C9B—H9B1	0.99
C1—C6	1.500 (4)	C9B—H9B2	0.99
C2—C3	1.383 (4)	C10B—H10D	0.98
C2—H2A	0.95	C10B—H10E	0.98
C3—N2	1.319 (4)	C10B—H10F	0.98
C3—H3	0.95	N1—N3	1.379 (3)
C4—N2	1.321 (4)	N1—H1	0.88
C4—C5	1.379 (4)	C11—C16	1.386 (4)
C4—H4A	0.95	C11—C12	1.403 (4)
C5—H5A	0.95	C11—C17	1.471 (3)
C6—O1	1.215 (3)	C12—O4	1.346 (3)
C6—N1	1.329 (4)	C12—C13	1.384 (3)
C7—C8	1.496 (5)	C13—C14	1.371 (4)
C7—H7A	0.98	C13—H13	0.95
C7—H7B	0.98	C14—O5	1.355 (3)
C7—H7C	0.98	C14—C15	1.397 (4)
C8—N3	1.273 (4)	C15—C16	1.371 (3)
C8—C9B	1.447 (18)	C15—H15	0.95
C8—C9A	1.526 (9)	C16—H16	0.95
C9A—C10A	1.445 (7)	C17—O3	1.232 (3)
C9A—H9A1	0.99	C17—O2	1.308 (3)
C9A—H9A2	0.99	O2—H2	0.84
C10A—H10A	0.98	O4—H4	0.84
C10A—H10B	0.98	O5—H5	0.84
C10A—H10C	0.98

C2—C1—C5	117.6 (2)	C10B—C9B—C8	105.9 (13)
C2—C1—C6	124.9 (2)	C10B—C9B—H9B1	110.6
C5—C1—C6	117.5 (3)	C8—C9B—H9B1	110.6
C1—C2—C3	118.8 (3)	C10B—C9B—H9B2	110.6
C1—C2—H2A	120.6	C8—C9B—H9B2	110.6
C3—C2—H2A	120.6	H9B1—C9B—H9B2	108.7
N2—C3—C2	123.8 (3)	C9B—C10B—H10D	109.5
N2—C3—H3	118.1	C9B—C10B—H10E	109.5
C2—C3—H3	118.1	H10D—C10B—H10E	109.5
N2—C4—C5	123.4 (3)	C9B—C10B—H10F	109.5
N2—C4—H4A	118.3	H10D—C10B—H10F	109.5
C5—C4—H4A	118.3	H10E—C10B—H10F	109.5
C1—C5—C4	119.4 (3)	C6—N1—N3	119.5 (3)
C1—C5—H5A	120.3	C6—N1—H1	120.2
C4—C5—H5A	120.3	N3—N1—H1	120.2
O1—C6—N1	123.3 (2)	C3—N2—C4	117.0 (2)
O1—C6—C1	120.5 (2)	C8—N3—N1	116.2 (3)
N1—C6—C1	116.3 (3)	C16—C11—C12	118.4 (2)
C8—C7—H7A	109.5	C16—C11—C17	122.1 (2)
C8—C7—H7B	109.5	C12—C11—C17	119.5 (2)
H7A—C7—H7B	109.5	O4—C12—C13	118.1 (2)
C8—C7—H7C	109.5	O4—C12—C11	121.9 (2)
H7A—C7—H7C	109.5	C13—C12—C11	120.1 (3)
H7B—C7—H7C	109.5	C14—C13—C12	120.1 (2)
N3—C8—C9B	133.3 (7)	C14—C13—H13	119.9
N3—C8—C7	125.0 (3)	C12—C13—H13	119.9
C9B—C8—C7	100.8 (6)	O5—C14—C13	117.7 (2)
N3—C8—C9A	112.6 (4)	O5—C14—C15	121.5 (2)
C7—C8—C9A	122.4 (4)	C13—C14—C15	120.8 (2)
C10A—C9A—C8	111.7 (6)	C16—C15—C14	118.7 (3)
C10A—C9A—H9A1	109.3	C16—C15—H15	120.7
C8—C9A—H9A1	109.3	C14—C15—H15	120.7
C10A—C9A—H9A2	109.3	C15—C16—C11	122.0 (3)
C8—C9A—H9A2	109.3	C15—C16—H16	119
H9A1—C9A—H9A2	107.9	C11—C16—H16	119
C9A—C10A—H10A	109.5	O3—C17—O2	122.1 (2)
C9A—C10A—H10B	109.5	O3—C17—C11	122.4 (3)
H10A—C10A—H10B	109.5	O2—C17—C11	115.5 (3)
C9A—C10A—H10C	109.5	C17—O2—H2	109.5
H10A—C10A—H10C	109.5	C12—O4—H4	109.5
H10B—C10A—H10C	109.5	C14—O5—H5	109.5

C5—C1—C2—C3	2.0 (4)	C9A—C8—N3—N1	174.3 (4)
C6—C1—C2—C3	−177.7 (3)	C6—N1—N3—C8	171.1 (3)
C1—C2—C3—N2	−0.6 (5)	C16—C11—C12—O4	179.1 (3)
C2—C1—C5—C4	−1.7 (5)	C17—C11—C12—O4	0.8 (4)
C6—C1—C5—C4	178.1 (3)	C16—C11—C12—C13	−0.1 (4)
N2—C4—C5—C1	−0.1 (5)	C17—C11—C12—C13	−178.5 (2)
C2—C1—C6—O1	179.6 (3)	O4—C12—C13—C14	−178.9 (3)
C5—C1—C6—O1	−0.2 (4)	C11—C12—C13—C14	0.4 (4)
C2—C1—C6—N1	−0.9 (4)	C12—C13—C14—O5	178.4 (3)
C5—C1—C6—N1	179.4 (3)	C12—C13—C14—C15	−0.3 (4)
N3—C8—C9A—C10A	116.4 (6)	O5—C14—C15—C16	−178.6 (3)
C7—C8—C9A—C10A	−65.7 (8)	C13—C14—C15—C16	0.1 (4)
N3—C8—C9B—C10B	2 (2)	C14—C15—C16—C11	0.2 (5)
C7—C8—C9B—C10B	−166.8 (13)	C12—C11—C16—C15	−0.1 (4)
O1—C6—N1—N3	−2.0 (4)	C17—C11—C16—C15	178.2 (3)
C1—C6—N1—N3	178.5 (2)	C16—C11—C17—O3	−179.7 (3)
C2—C3—N2—C4	−1.1 (5)	C12—C11—C17—O3	−1.4 (4)
C5—C4—N2—C3	1.5 (5)	C16—C11—C17—O2	−1.0 (4)
C9B—C8—N3—N1	−170.6 (12)	C12—C11—C17—O2	177.3 (2)
C7—C8—N3—N1	−3.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.88	2.58	3.124 (3)	121
O2—H2···N2	0.84	1.8	2.633 (3)	175
C4—H4A···O3	0.95	2.56	3.233 (3)	128
O4—H4···O3	0.84	1.82	2.568 (3)	147
O5—H5···O1ⁱⁱ	0.84	1.85	2.665 (3)	163

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+3/2, −y+1/2, z+1/2.

N'-(Propan-2-ylidene)pyridine-4-carbohydrazide; 1-naphthoic acid (izact1nta) top

Crystal data top

C₉H₁₁N₃O·C₁₁H₈O₂	F(000) = 736
M_r = 349.38	D_x = 1.354 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 9944 reflections
a = 7.6312 (3) Å	θ = 2.4–32.0°
b = 33.5293 (12) Å	µ = 0.09 mm⁻¹
c = 7.3493 (3) Å	T = 173 K
β = 114.298 (1)°	Plate, colourless
V = 1713.88 (12) Å³	0.72 × 0.33 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	6145 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.056
Absorption correction: multi-scan (SADABS; Sheldrick, 2001; Krause et al., 2015)	θ_max = 33.7°, θ_min = 2.4°
T_min = 0.684, T_max = 0.747	h = −11→11
39441 measured reflections	k = −52→52
6819 independent reflections	l = −11→11

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0746P)² + 0.0558P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.122	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.33 e Å⁻³
6819 reflections	Δρ_min = −0.17 e Å⁻³
238 parameters	Absolute structure: Flack x determined using 2626 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.0 (3)
0 constraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4245 (2)	0.64077 (4)	0.5306 (3)	0.0271 (3)
H1	0.427394	0.612495	0.5399	0.033*
C2	0.2532 (2)	0.66022 (4)	0.4942 (2)	0.0245 (3)
H2	0.140806	0.645537	0.476333	0.029*
C3	0.2488 (2)	0.70167 (4)	0.4844 (2)	0.0213 (2)
C4	0.4160 (2)	0.72176 (4)	0.5094 (2)	0.0268 (3)
H4	0.417923	0.750066	0.504539	0.032*
C5	0.5808 (2)	0.69982 (5)	0.5418 (3)	0.0294 (3)
H5	0.694221	0.713739	0.556449	0.035*
C6	0.0586 (2)	0.72170 (4)	0.4316 (2)	0.0231 (2)
C7	−0.1291 (2)	0.81130 (4)	0.4976 (2)	0.0270 (3)
C8	0.0322 (3)	0.84017 (5)	0.5454 (3)	0.0378 (4)
H8A	0.099418	0.843103	0.690592	0.057*
H8B	−0.018815	0.866102	0.485523	0.057*
H8C	0.122164	0.830294	0.491653	0.057*
C9	−0.3242 (3)	0.82752 (6)	0.4609 (3)	0.0387 (4)
H9A	−0.325317	0.836275	0.587683	0.058*
H9B	−0.421165	0.806654	0.402073	0.058*
H9C	−0.353539	0.850212	0.369082	0.058*
C10	0.98959 (19)	0.54175 (4)	0.6266 (2)	0.0229 (3)
C11	1.1694 (2)	0.55617 (5)	0.6594 (2)	0.0275 (3)
H11	1.18928	0.584175	0.662443	0.033*
C12	1.3245 (2)	0.53034 (5)	0.6887 (3)	0.0330 (3)
H12	1.44702	0.54094	0.710834	0.04*
C13	1.2980 (2)	0.49021 (5)	0.6851 (3)	0.0321 (3)
H13	1.402665	0.472883	0.704124	0.039*
C14	1.1176 (2)	0.47396 (5)	0.6536 (2)	0.0263 (3)
C15	0.9586 (2)	0.49954 (4)	0.6251 (2)	0.0228 (2)
C16	0.7820 (2)	0.48134 (5)	0.5987 (3)	0.0307 (3)
H16	0.674184	0.497554	0.581332	0.037*
C17	0.7649 (3)	0.44058 (5)	0.5979 (3)	0.0362 (4)
H17	0.645341	0.429103	0.580891	0.043*
C18	0.9200 (3)	0.41547 (5)	0.6216 (3)	0.0375 (4)
H18	0.905031	0.38732	0.618488	0.045*
C19	1.0922 (3)	0.43199 (5)	0.6491 (3)	0.0340 (3)
H19	1.197449	0.415057	0.665593	0.041*
C20	0.8321 (2)	0.57131 (4)	0.5883 (2)	0.0249 (3)
N1	0.58678 (19)	0.65991 (4)	0.5534 (2)	0.0284 (3)
N2	0.06057 (18)	0.75731 (4)	0.5167 (2)	0.0249 (2)
H2A	0.168276	0.76959	0.591197	0.03*
N3	−0.12045 (19)	0.77355 (4)	0.4788 (2)	0.0270 (3)
O1	−0.08842 (17)	0.70564 (3)	0.3110 (2)	0.0312 (3)
O2	0.89085 (18)	0.60918 (3)	0.6040 (2)	0.0338 (3)
H2B	0.797958	0.62443	0.58666	0.051*
O3	0.66461 (19)	0.56323 (4)	0.5423 (3)	0.0446 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0247 (6)	0.0208 (5)	0.0370 (7)	0.0017 (5)	0.0138 (6)	0.0004 (5)
C2	0.0205 (6)	0.0196 (5)	0.0317 (7)	−0.0001 (4)	0.0090 (5)	0.0007 (5)
C3	0.0190 (5)	0.0195 (5)	0.0236 (6)	0.0011 (4)	0.0069 (5)	0.0001 (5)
C4	0.0251 (6)	0.0204 (5)	0.0359 (8)	−0.0021 (5)	0.0137 (6)	−0.0015 (5)
C5	0.0240 (7)	0.0260 (6)	0.0415 (8)	−0.0031 (5)	0.0169 (6)	−0.0027 (6)
C6	0.0199 (6)	0.0187 (5)	0.0274 (6)	0.0004 (4)	0.0064 (5)	0.0021 (5)
C7	0.0292 (7)	0.0231 (6)	0.0262 (6)	0.0057 (5)	0.0088 (6)	0.0027 (5)
C8	0.0355 (9)	0.0235 (7)	0.0441 (10)	−0.0003 (6)	0.0062 (7)	0.0027 (6)
C9	0.0390 (9)	0.0343 (8)	0.0450 (10)	0.0149 (7)	0.0195 (8)	0.0070 (7)
C10	0.0184 (6)	0.0237 (6)	0.0272 (6)	0.0007 (4)	0.0100 (5)	−0.0006 (5)
C11	0.0196 (6)	0.0282 (7)	0.0352 (7)	−0.0008 (5)	0.0117 (6)	0.0042 (6)
C12	0.0199 (6)	0.0389 (8)	0.0415 (9)	0.0038 (6)	0.0138 (6)	0.0094 (7)
C13	0.0246 (7)	0.0364 (8)	0.0373 (8)	0.0094 (6)	0.0147 (6)	0.0083 (6)
C14	0.0266 (7)	0.0263 (6)	0.0263 (6)	0.0056 (5)	0.0113 (6)	0.0037 (5)
C15	0.0211 (6)	0.0223 (6)	0.0247 (6)	0.0008 (5)	0.0091 (5)	−0.0005 (5)
C16	0.0252 (7)	0.0242 (6)	0.0422 (9)	−0.0023 (5)	0.0133 (6)	−0.0025 (6)
C17	0.0316 (8)	0.0253 (7)	0.0475 (10)	−0.0054 (6)	0.0121 (7)	−0.0022 (6)
C18	0.0416 (9)	0.0223 (7)	0.0428 (9)	0.0002 (6)	0.0115 (8)	−0.0022 (6)
C19	0.0377 (9)	0.0255 (7)	0.0368 (8)	0.0089 (6)	0.0134 (7)	0.0025 (6)
C20	0.0212 (6)	0.0213 (6)	0.0338 (7)	−0.0011 (5)	0.0129 (5)	−0.0033 (5)
N1	0.0233 (6)	0.0260 (6)	0.0386 (7)	0.0013 (5)	0.0155 (5)	−0.0018 (5)
N2	0.0189 (5)	0.0204 (5)	0.0307 (6)	0.0019 (4)	0.0054 (5)	−0.0012 (4)
N3	0.0214 (5)	0.0241 (6)	0.0337 (7)	0.0038 (4)	0.0095 (5)	0.0017 (4)
O1	0.0211 (5)	0.0240 (5)	0.0382 (6)	0.0005 (4)	0.0017 (4)	−0.0036 (4)
O2	0.0219 (5)	0.0207 (5)	0.0578 (8)	−0.0017 (4)	0.0152 (5)	−0.0047 (5)
O3	0.0235 (6)	0.0256 (5)	0.0863 (12)	−0.0018 (4)	0.0242 (6)	−0.0063 (6)

Geometric parameters (Å, º) top

C1—N1	1.342 (2)	C10—C15	1.4344 (19)
C1—C2	1.385 (2)	C10—C20	1.4923 (19)
C1—H1	0.95	C11—C12	1.409 (2)
C2—C3	1.3914 (18)	C11—H11	0.95
C2—H2	0.95	C12—C13	1.359 (2)
C3—C4	1.386 (2)	C12—H12	0.95
C3—C6	1.4987 (19)	C13—C14	1.409 (2)
C4—C5	1.390 (2)	C13—H13	0.95
C4—H4	0.95	C14—C19	1.419 (2)
C5—N1	1.340 (2)	C14—C15	1.4293 (19)
C5—H5	0.95	C15—C16	1.418 (2)
C6—O1	1.2311 (18)	C16—C17	1.372 (2)
C6—N2	1.3450 (18)	C16—H16	0.95
C7—N3	1.2778 (19)	C17—C18	1.403 (3)
C7—C8	1.490 (2)	C17—H17	0.95
C7—C9	1.501 (2)	C18—C19	1.362 (3)
C8—H8A	0.98	C18—H18	0.95
C8—H8B	0.98	C19—H19	0.95
C8—H8C	0.98	C20—O3	1.2109 (18)
C9—H9A	0.98	C20—O2	1.3357 (17)
C9—H9B	0.98	N2—N3	1.4021 (17)
C9—H9C	0.98	N2—H2A	0.88
C10—C11	1.3794 (19)	O2—H2B	0.84

N1—C1—C2	123.21 (13)	C10—C11—C12	121.57 (14)
N1—C1—H1	118.4	C10—C11—H11	119.2
C2—C1—H1	118.4	C12—C11—H11	119.2
C1—C2—C3	118.74 (13)	C13—C12—C11	119.80 (15)
C1—C2—H2	120.6	C13—C12—H12	120.1
C3—C2—H2	120.6	C11—C12—H12	120.1
C4—C3—C2	118.52 (12)	C12—C13—C14	120.87 (14)
C4—C3—C6	123.86 (12)	C12—C13—H13	119.6
C2—C3—C6	117.45 (12)	C14—C13—H13	119.6
C3—C4—C5	118.92 (12)	C13—C14—C19	120.15 (14)
C3—C4—H4	120.5	C13—C14—C15	120.38 (14)
C5—C4—H4	120.5	C19—C14—C15	119.47 (14)
N1—C5—C4	122.97 (13)	C16—C15—C14	117.61 (13)
N1—C5—H5	118.5	C16—C15—C10	124.78 (13)
C4—C5—H5	118.5	C14—C15—C10	117.61 (13)
O1—C6—N2	123.76 (14)	C17—C16—C15	120.83 (15)
O1—C6—C3	119.27 (13)	C17—C16—H16	119.6
N2—C6—C3	116.95 (12)	C15—C16—H16	119.6
N3—C7—C8	126.46 (15)	C16—C17—C18	121.53 (16)
N3—C7—C9	115.53 (15)	C16—C17—H17	119.2
C8—C7—C9	117.98 (14)	C18—C17—H17	119.2
C7—C8—H8A	109.5	C19—C18—C17	119.15 (15)
C7—C8—H8B	109.5	C19—C18—H18	120.4
H8A—C8—H8B	109.5	C17—C18—H18	120.4
C7—C8—H8C	109.5	C18—C19—C14	121.39 (15)
H8A—C8—H8C	109.5	C18—C19—H19	119.3
H8B—C8—H8C	109.5	C14—C19—H19	119.3
C7—C9—H9A	109.5	O3—C20—O2	120.99 (13)
C7—C9—H9B	109.5	O3—C20—C10	125.43 (13)
H9A—C9—H9B	109.5	O2—C20—C10	113.56 (12)
C7—C9—H9C	109.5	C5—N1—C1	117.63 (13)
H9A—C9—H9C	109.5	C6—N2—N3	115.52 (12)
H9B—C9—H9C	109.5	C6—N2—H2A	122.2
C11—C10—C15	119.76 (12)	N3—N2—H2A	122.2
C11—C10—C20	117.79 (13)	C7—N3—N2	117.00 (13)
C15—C10—C20	122.43 (12)	C20—O2—H2B	109.5

N1—C1—C2—C3	−1.3 (3)	C20—C10—C15—C16	−3.5 (2)
C1—C2—C3—C4	0.6 (2)	C11—C10—C15—C14	−1.5 (2)
C1—C2—C3—C6	176.11 (14)	C20—C10—C15—C14	176.86 (13)
C2—C3—C4—C5	0.5 (2)	C14—C15—C16—C17	−0.9 (2)
C6—C3—C4—C5	−174.67 (14)	C10—C15—C16—C17	179.51 (16)
C3—C4—C5—N1	−1.1 (3)	C15—C16—C17—C18	−0.5 (3)
C4—C3—C6—O1	139.64 (16)	C16—C17—C18—C19	1.0 (3)
C2—C3—C6—O1	−35.6 (2)	C17—C18—C19—C14	−0.2 (3)
C4—C3—C6—N2	−38.5 (2)	C13—C14—C19—C18	179.09 (18)
C2—C3—C6—N2	146.30 (14)	C15—C14—C19—C18	−1.1 (3)
C15—C10—C11—C12	1.1 (2)	C11—C10—C20—O3	174.12 (18)
C20—C10—C11—C12	−177.37 (15)	C15—C10—C20—O3	−4.3 (2)
C10—C11—C12—C13	−0.1 (3)	C11—C10—C20—O2	−4.2 (2)
C11—C12—C13—C14	−0.4 (3)	C15—C10—C20—O2	177.43 (14)
C12—C13—C14—C19	179.62 (17)	C4—C5—N1—C1	0.6 (3)
C12—C13—C14—C15	−0.1 (2)	C2—C1—N1—C5	0.6 (3)
C13—C14—C15—C16	−178.58 (15)	O1—C6—N2—N3	7.5 (2)
C19—C14—C15—C16	1.7 (2)	C3—C6—N2—N3	−174.42 (12)
C13—C14—C15—C10	1.1 (2)	C8—C7—N3—N2	3.5 (2)
C19—C14—C15—C10	−178.71 (15)	C9—C7—N3—N2	−178.53 (14)
C11—C10—C15—C16	178.10 (15)	C6—N2—N3—C7	−157.47 (14)

N'-(Butan-2-ylidene)pyridine-4-carbohydrazide; 2-chloro-4-nitrobenzoic acid (izbt2c4n) top

Crystal data top

C₇H₄ClNO₄·C₁₀H₁₃N₃O	F(000) = 816
M_r = 392.79	D_x = 1.483 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9966 reflections
a = 7.2682 (3) Å	θ = 2.4–30.8°
b = 34.0775 (15) Å	µ = 0.26 mm⁻¹
c = 7.6124 (3) Å	T = 173 K
β = 111.081 (2)°	Plate, colourless
V = 1759.27 (13) Å³	0.46 × 0.26 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.081
φ and ω scans	θ_max = 31.1°, θ_min = 2.4°
111394 measured reflections	h = −10→10
5624 independent reflections	k = −49→49
5056 reflections with I > 2σ(I)	l = −11→11

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: mixed
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0581P)² + 0.7134P] where P = (F_o² + 2F_c²)/3
5624 reflections	(Δ/σ)_max = 0.002
250 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³
0 constraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.34552 (19)	0.70488 (4)	0.34294 (16)	0.0265 (2)
H1	0.338196	0.718339	0.231343	0.032*
C2	0.36445 (17)	0.72661 (3)	0.50281 (16)	0.0236 (2)
H2A	0.368392	0.754461	0.500126	0.028*
C3	0.37753 (15)	0.70697 (3)	0.66653 (14)	0.01940 (19)
C4	0.37152 (18)	0.66621 (3)	0.66495 (16)	0.0239 (2)
H4	0.382589	0.651968	0.77559	0.029*
C5	0.34909 (19)	0.64679 (4)	0.49885 (18)	0.0281 (2)
H5	0.341789	0.61895	0.496836	0.034*
C6	0.41408 (16)	0.72790 (3)	0.84962 (14)	0.01968 (19)
C7	0.35850 (16)	0.82289 (3)	0.97889 (16)	0.0224 (2)
C8	0.3268 (2)	0.84432 (4)	0.79821 (18)	0.0308 (3)
H8A	0.398513	0.830927	0.728525	0.046*
H8B	0.375439	0.871288	0.826095	0.046*
H8C	0.185714	0.844755	0.721955	0.046*
C9	0.38785 (18)	0.84802 (3)	1.14869 (17)	0.0252 (2)
H9A	0.270812	0.865116	1.122133	0.03*
H9B	0.502954	0.865278	1.167495	0.03*
C10	0.4201 (2)	0.82623 (4)	1.33066 (18)	0.0306 (3)
H10A	0.303647	0.81027	1.317269	0.046*
H10B	0.441788	0.84514	1.43314	0.046*
H10C	0.535749	0.809159	1.35937	0.046*
C11	0.2577 (2)	0.55646 (4)	−0.06804 (19)	0.0329 (3)
C12	0.4153 (2)	0.55063 (4)	−0.12851 (19)	0.0359 (3)
C13	0.4172 (3)	0.51828 (4)	−0.2402 (2)	0.0497 (5)
H13	0.524522	0.513935	−0.281211	0.06*
C14	0.2596 (4)	0.49280 (4)	−0.2897 (2)	0.0552 (5)
C15	0.1001 (3)	0.49746 (5)	−0.2356 (2)	0.0532 (5)
H15	−0.006369	0.479348	−0.272787	0.064*
C16	0.1008 (3)	0.52969 (4)	−0.1245 (2)	0.0429 (4)
H16	−0.008083	0.533764	−0.085449	0.051*
C17	0.2412 (2)	0.58813 (4)	0.0638 (2)	0.0339 (3)
Cl01	0.62203 (6)	0.58034 (2)	−0.06254 (6)	0.04457 (12)
N1	0.33722 (16)	0.66570 (3)	0.34045 (15)	0.0273 (2)
N2	0.33516 (15)	0.76384 (3)	0.83540 (13)	0.02305 (19)
H2	0.264867	0.773703	0.724711	0.028*
N3	0.36705 (15)	0.78542 (3)	1.00102 (13)	0.02341 (19)
N4	0.2662 (4)	0.45802 (4)	−0.4029 (2)	0.0803 (8)
O1	0.51772 (13)	0.71240 (2)	0.99850 (11)	0.02553 (18)
O2	0.33658 (16)	0.62034 (3)	0.06437 (13)	0.0320 (2)
O3	0.1408 (3)	0.58288 (4)	0.1583 (3)	0.0712 (5)
O4	0.4196 (5)	0.45158 (5)	−0.4308 (3)	0.1193 (10)
O5	0.1146 (4)	0.43750 (4)	−0.4613 (2)	0.0987 (8)
H2B	0.326 (4)	0.6369 (7)	0.163 (4)	0.075 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0313 (6)	0.0300 (6)	0.0208 (5)	0.0006 (4)	0.0124 (4)	−0.0006 (4)
C2	0.0288 (5)	0.0221 (5)	0.0216 (5)	0.0003 (4)	0.0111 (4)	0.0005 (4)
C3	0.0186 (4)	0.0216 (5)	0.0174 (4)	0.0007 (3)	0.0058 (4)	−0.0007 (3)
C4	0.0277 (5)	0.0213 (5)	0.0217 (5)	0.0014 (4)	0.0077 (4)	0.0004 (4)
C5	0.0338 (6)	0.0226 (5)	0.0280 (6)	0.0006 (4)	0.0111 (5)	−0.0040 (4)
C6	0.0202 (4)	0.0208 (5)	0.0171 (4)	−0.0010 (4)	0.0055 (4)	−0.0004 (3)
C7	0.0212 (5)	0.0239 (5)	0.0210 (5)	−0.0006 (4)	0.0063 (4)	−0.0018 (4)
C8	0.0407 (7)	0.0259 (5)	0.0234 (5)	−0.0039 (5)	0.0085 (5)	0.0009 (4)
C9	0.0292 (5)	0.0228 (5)	0.0243 (5)	−0.0011 (4)	0.0107 (4)	−0.0033 (4)
C10	0.0371 (6)	0.0318 (6)	0.0242 (5)	−0.0035 (5)	0.0127 (5)	−0.0014 (4)
C11	0.0482 (8)	0.0233 (5)	0.0264 (6)	0.0043 (5)	0.0123 (5)	−0.0024 (4)
C12	0.0565 (9)	0.0266 (6)	0.0269 (6)	0.0121 (6)	0.0178 (6)	0.0037 (5)
C13	0.0922 (14)	0.0308 (7)	0.0333 (7)	0.0233 (8)	0.0313 (8)	0.0064 (6)
C14	0.1142 (17)	0.0216 (6)	0.0247 (6)	0.0129 (8)	0.0189 (8)	−0.0011 (5)
C15	0.0877 (14)	0.0268 (7)	0.0341 (8)	−0.0060 (8)	0.0087 (8)	−0.0048 (6)
C16	0.0588 (10)	0.0281 (6)	0.0367 (7)	−0.0036 (6)	0.0111 (7)	−0.0052 (5)
C17	0.0411 (7)	0.0288 (6)	0.0351 (7)	−0.0022 (5)	0.0176 (6)	−0.0086 (5)
Cl01	0.0506 (2)	0.0406 (2)	0.0516 (2)	0.01217 (15)	0.02936 (18)	0.00589 (15)
N1	0.0296 (5)	0.0295 (5)	0.0239 (5)	0.0001 (4)	0.0109 (4)	−0.0059 (4)
N2	0.0280 (5)	0.0215 (4)	0.0159 (4)	0.0033 (3)	0.0035 (3)	−0.0019 (3)
N3	0.0259 (5)	0.0242 (4)	0.0180 (4)	0.0014 (3)	0.0053 (3)	−0.0039 (3)
N4	0.180 (2)	0.0260 (7)	0.0347 (7)	0.0174 (10)	0.0383 (11)	−0.0012 (6)
O1	0.0293 (4)	0.0247 (4)	0.0179 (4)	0.0024 (3)	0.0028 (3)	0.0015 (3)
O2	0.0455 (5)	0.0255 (4)	0.0291 (4)	−0.0021 (4)	0.0184 (4)	−0.0069 (3)
O3	0.0978 (12)	0.0514 (8)	0.0994 (12)	−0.0357 (8)	0.0777 (11)	−0.0389 (8)
O4	0.243 (3)	0.0530 (10)	0.0986 (15)	0.0310 (14)	0.1064 (19)	−0.0144 (9)
O5	0.199 (2)	0.0292 (6)	0.0447 (8)	0.0000 (10)	0.0163 (11)	−0.0110 (6)

Geometric parameters (Å, º) top

C1—N1	1.3361 (16)	C10—H10A	0.98
C1—C2	1.3885 (16)	C10—H10B	0.98
C1—H1	0.95	C10—H10C	0.98
C2—C3	1.3874 (15)	C11—C12	1.394 (2)
C2—H2A	0.95	C11—C16	1.402 (2)
C3—C4	1.3897 (15)	C11—C17	1.5076 (18)
C3—C6	1.5019 (14)	C12—C13	1.396 (2)
C4—C5	1.3838 (16)	C12—Cl01	1.7297 (17)
C4—H4	0.95	C13—C14	1.377 (3)
C5—N1	1.3423 (16)	C13—H13	0.95
C5—H5	0.95	C14—C15	1.372 (3)
C6—O1	1.2316 (13)	C14—N4	1.476 (2)
C6—N2	1.3400 (14)	C15—C16	1.385 (2)
C7—N3	1.2865 (15)	C15—H15	0.95
C7—C8	1.5001 (16)	C16—H16	0.95
C7—C9	1.5004 (16)	C17—O3	1.2077 (19)
C8—H8A	0.98	C17—O2	1.2974 (17)
C8—H8B	0.98	N2—N3	1.4051 (13)
C8—H8C	0.98	N2—H2	0.88
C9—C10	1.5139 (17)	N4—O4	1.228 (4)
C9—H9A	0.99	N4—O5	1.244 (3)
C9—H9B	0.99	O2—H2B	0.96 (3)

N1—C1—C2	122.35 (11)	H10A—C10—H10B	109.5
N1—C1—H1	118.8	C9—C10—H10C	109.5
C2—C1—H1	118.8	H10A—C10—H10C	109.5
C3—C2—C1	118.89 (11)	H10B—C10—H10C	109.5
C3—C2—H2A	120.6	C12—C11—C16	118.74 (13)
C1—C2—H2A	120.6	C12—C11—C17	126.39 (13)
C2—C3—C4	118.86 (10)	C16—C11—C17	114.78 (14)
C2—C3—C6	122.45 (10)	C11—C12—C13	120.22 (16)
C4—C3—C6	118.51 (9)	C11—C12—Cl01	123.50 (11)
C5—C4—C3	118.61 (11)	C13—C12—Cl01	116.19 (14)
C5—C4—H4	120.7	C14—C13—C12	118.36 (18)
C3—C4—H4	120.7	C14—C13—H13	120.8
N1—C5—C4	122.66 (11)	C12—C13—H13	120.8
N1—C5—H5	118.7	C15—C14—C13	123.66 (14)
C4—C5—H5	118.7	C15—C14—N4	118.4 (2)
O1—C6—N2	124.65 (10)	C13—C14—N4	117.9 (2)
O1—C6—C3	119.72 (10)	C14—C15—C16	117.22 (18)
N2—C6—C3	115.56 (9)	C14—C15—H15	121.4
N3—C7—C8	125.98 (10)	C16—C15—H15	121.4
N3—C7—C9	117.93 (10)	C15—C16—C11	121.79 (18)
C8—C7—C9	116.07 (10)	C15—C16—H16	119.1
C7—C8—H8A	109.5	C11—C16—H16	119.1
C7—C8—H8B	109.5	O3—C17—O2	124.04 (13)
H8A—C8—H8B	109.5	O3—C17—C11	120.00 (13)
C7—C8—H8C	109.5	O2—C17—C11	115.95 (12)
H8A—C8—H8C	109.5	C1—N1—C5	118.62 (10)
H8B—C8—H8C	109.5	C6—N2—N3	118.58 (9)
C7—C9—C10	115.82 (10)	C6—N2—H2	120.7
C7—C9—H9A	108.3	N3—N2—H2	120.7
C10—C9—H9A	108.3	C7—N3—N2	114.68 (10)
C7—C9—H9B	108.3	O4—N4—O5	125.48 (19)
C10—C9—H9B	108.3	O4—N4—C14	117.8 (2)
H9A—C9—H9B	107.4	O5—N4—C14	116.7 (2)
C9—C10—H10A	109.5	C17—O2—H2B	107.9 (15)
C9—C10—H10B	109.5

N1—C1—C2—C3	0.76 (18)	C13—C14—C15—C16	−0.3 (3)
C1—C2—C3—C4	0.10 (17)	N4—C14—C15—C16	178.00 (15)
C1—C2—C3—C6	175.11 (10)	C14—C15—C16—C11	−0.4 (2)
C2—C3—C4—C5	−1.16 (17)	C12—C11—C16—C15	1.1 (2)
C6—C3—C4—C5	−176.37 (11)	C17—C11—C16—C15	−175.78 (14)
C3—C4—C5—N1	1.49 (19)	C12—C11—C17—O3	−153.35 (18)
C2—C3—C6—O1	−143.50 (12)	C16—C11—C17—O3	23.2 (2)
C4—C3—C6—O1	31.53 (15)	C12—C11—C17—O2	27.9 (2)
C2—C3—C6—N2	33.63 (15)	C16—C11—C17—O2	−155.51 (13)
C4—C3—C6—N2	−151.34 (11)	C2—C1—N1—C5	−0.49 (19)
N3—C7—C9—C10	−1.45 (16)	C4—C5—N1—C1	−0.66 (19)
C8—C7—C9—C10	−179.90 (11)	O1—C6—N2—N3	−1.73 (17)
C16—C11—C12—C13	−1.1 (2)	C3—C6—N2—N3	−178.70 (9)
C17—C11—C12—C13	175.29 (14)	C8—C7—N3—N2	−2.66 (17)
C16—C11—C12—Cl01	−177.59 (11)	C9—C7—N3—N2	179.06 (10)
C17—C11—C12—Cl01	−1.2 (2)	C6—N2—N3—C7	153.96 (11)
C11—C12—C13—C14	0.6 (2)	C15—C14—N4—O4	−171.23 (19)
Cl01—C12—C13—C14	177.25 (11)	C13—C14—N4—O4	7.1 (3)
C12—C13—C14—C15	0.2 (2)	C15—C14—N4—O5	8.4 (2)
C12—C13—C14—N4	−178.11 (13)	C13—C14—N4—O5	−173.23 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.88	2.05	2.8809 (13)	158
C4—H4···O2ⁱⁱ	0.95	2.58	3.5082 (15)	167
C1—H1···O1ⁱⁱⁱ	0.95	2.56	3.2966 (15)	135
C8—H8B···O5^iv	0.98	2.47	3.380 (2)	154
C8—H8C···O1ⁱ	0.98	2.59	3.2095 (15)	122
C13—H13···O4^v	0.95	2.64	3.297 (3)	126
C15—H15···O3^vi	0.95	2.61	3.413 (2)	142
O2—H2B···N1	0.96 (3)	1.65 (3)	2.6076 (13)	173 (2)
N2—H2···O1ⁱ	0.88	2.05	2.8809 (13)	158
C4—H4···O2ⁱⁱ	0.95	2.58	3.5082 (15)	167
C1—H1···O1ⁱⁱⁱ	0.95	2.56	3.2966 (15)	135
C8—H8B···O5^iv	0.98	2.47	3.380 (2)	154
C8—H8C···O1ⁱ	0.98	2.59	3.2095 (15)	122
C13—H13···O4^v	0.95	2.64	3.297 (3)	126
C15—H15···O3^vi	0.95	2.61	3.413 (2)	142
O2—H2B···N1	0.96 (3)	1.65 (3)	2.6076 (13)	173 (2)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, y, z+1; (iii) x, y, z−1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z−1; (vi) −x, −y+1, −z.

N'-(Butan-2-ylidene)pyridine-4-carbohydrazide; 2,5-dihydroxybenzoic acid (izbt25dhba) top

Crystal data top

C₁₀H₁₃N₃O·C₇H₆O₄	Z = 4
M_r = 345.35	F(000) = 728
Triclinic, P1	D_x = 1.383 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2054 (3) Å	Cell parameters from 9903 reflections
b = 11.5589 (4) Å	θ = 2.2–27.3°
c = 15.6268 (6) Å	µ = 0.10 mm⁻¹
α = 92.383 (2)°	T = 123 K
β = 93.092 (2)°	Plate, colourless
γ = 90.666 (2)°	0.45 × 0.38 × 0.13 mm
V = 1658.74 (10) Å³

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.079
φ and ω scans	θ_max = 28°, θ_min = 1.8°
73254 measured reflections	h = −12→12
8026 independent reflections	k = −15→15
5972 reflections with I > 2σ(I)	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: mixed
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0779P)² + 1.3095P] where P = (F_o² + 2F_c²)/3
8026 reflections	(Δ/σ)_max < 0.001
506 parameters	Δρ_max = 1.33 e Å⁻³
21 restraints	Δρ_min = −0.68 e Å⁻³
0 constraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2112 (3)	0.59980 (18)	0.42485 (14)	0.0394 (5)
H1	0.228948	0.524065	0.444016	0.047*
C2	0.1065 (2)	0.61362 (17)	0.36000 (14)	0.0350 (4)
H2	0.05337	0.548625	0.335013	0.042*
C3	0.0796 (2)	0.72412 (16)	0.33160 (13)	0.0302 (4)
C4	0.1587 (2)	0.81679 (16)	0.37099 (13)	0.0315 (4)
H4	0.141596	0.893651	0.354046	0.038*
C5	0.2624 (2)	0.79498 (17)	0.43507 (14)	0.0332 (4)
H5	0.317352	0.858236	0.461266	0.04*
C6	−0.0350 (2)	0.75020 (17)	0.26420 (15)	0.0349 (4)
C7	−0.2250 (4)	0.5985 (2)	0.0953 (2)	0.0687 (9)
C8	−0.1519 (4)	0.4878 (2)	0.0876 (2)	0.0647 (8)
H8A	−0.04954	0.501106	0.076189	0.097*
H8B	−0.199055	0.440653	0.04015	0.097*
H8C	−0.158024	0.447199	0.141079	0.097*
C9	−0.3335 (6)	0.6135 (4)	0.0212 (3)	0.0541 (16)	0.625 (10)
H9A	−0.288822	0.587217	−0.032332	0.065*	0.625 (10)
H9B	−0.418717	0.562531	0.028434	0.065*	0.625 (10)
C10	−0.3857 (7)	0.7345 (6)	0.0110 (4)	0.074 (2)	0.625 (10)
H10A	−0.461649	0.734997	−0.035398	0.111*	0.625 (10)
H10B	−0.304234	0.784378	−0.002877	0.111*	0.625 (10)
H10C	−0.425497	0.763312	0.064652	0.111*	0.625 (10)
C11	0.6568 (2)	0.73609 (16)	0.68602 (14)	0.0332 (4)
C12	0.7330 (2)	0.83240 (17)	0.72385 (17)	0.0407 (5)
C13	0.8377 (3)	0.81677 (18)	0.78881 (18)	0.0451 (6)
H13	0.89199	0.881548	0.813175	0.054*
C14	0.8644 (3)	0.70739 (19)	0.81880 (17)	0.0423 (5)
H14	0.936431	0.697752	0.863681	0.051*
C15	0.7863 (2)	0.61188 (16)	0.78356 (14)	0.0337 (4)
C16	0.6847 (2)	0.62589 (16)	0.71685 (13)	0.0318 (4)
H16	0.633109	0.560325	0.69155	0.038*
C17	0.5472 (3)	0.75068 (18)	0.61543 (14)	0.0375 (5)
C18	0.2402 (2)	0.30223 (17)	0.56766 (15)	0.0378 (5)
H18	0.184874	0.361575	0.541748	0.045*
C19	0.3424 (2)	0.33290 (17)	0.63206 (15)	0.0373 (5)
H19	0.358276	0.411827	0.649888	0.045*
C20	0.4225 (2)	0.24569 (17)	0.67075 (16)	0.0365 (5)
C21	0.3967 (2)	0.13173 (17)	0.64134 (17)	0.0411 (5)
H21	0.450213	0.070407	0.665901	0.049*
C22	0.2930 (3)	0.10924 (18)	0.57636 (16)	0.0430 (5)
H22	0.275925	0.031203	0.556543	0.052*
C23	0.5371 (2)	0.28117 (18)	0.73810 (17)	0.0405 (5)
C24	0.7335 (3)	0.1562 (2)	0.9060 (2)	0.0587 (7)
C25	0.6514 (4)	0.0440 (2)	0.9189 (2)	0.0685 (9)
H25A	0.698797	0.00369	0.966535	0.103*
H25B	0.550861	0.061286	0.931974	0.103*
H25C	0.651695	−0.005447	0.866372	0.103*
C26	0.8651 (4)	0.1869 (3)	0.9665 (3)	0.0792 (10)
H26A	0.896188	0.267519	0.957394	0.095*
H26B	0.836178	0.183245	1.026426	0.095*
C27A	0.9875 (6)	0.1110 (6)	0.9547 (4)	0.108 (2)	0.773 (9)
H27A	1.068248	0.135148	0.995175	0.161*	0.773 (9)
H27B	0.958489	0.031188	0.964948	0.161*	0.773 (9)
H27C	1.018548	0.11553	0.895861	0.161*	0.773 (9)
C27B	0.988 (2)	0.239 (3)	0.932 (2)	0.164 (10)	0.227 (9)
H27D	1.063797	0.254299	0.977489	0.246*	0.227 (9)
H27E	1.025203	0.187517	0.887217	0.246*	0.227 (9)
H27F	0.959234	0.312707	0.906915	0.246*	0.227 (9)
C28	−0.1528 (2)	0.21103 (17)	0.31637 (15)	0.0359 (5)
C29	−0.2306 (3)	0.30216 (18)	0.28099 (18)	0.0444 (6)
C30	−0.3371 (3)	0.2784 (2)	0.2164 (2)	0.0506 (6)
H30	−0.393105	0.339704	0.193844	0.061*
C31	−0.3626 (3)	0.1658 (2)	0.18448 (19)	0.0472 (6)
H31	−0.435107	0.150553	0.139709	0.057*
C32	−0.2823 (2)	0.07531 (17)	0.21785 (15)	0.0374 (5)
C33	−0.1794 (2)	0.09764 (17)	0.28375 (14)	0.0342 (4)
H33	−0.125851	0.035639	0.307325	0.041*
C34	−0.0415 (3)	0.23411 (18)	0.38673 (15)	0.0394 (5)
N1	0.2889 (2)	0.68817 (15)	0.46199 (11)	0.0370 (4)
N2	−0.0756 (2)	0.66280 (16)	0.20764 (14)	0.0439 (5)
N3	−0.1888 (3)	0.6817 (2)	0.1479 (2)	0.0776 (9)
N4	0.2149 (2)	0.19217 (15)	0.53972 (13)	0.0401 (4)
N5	0.5822 (2)	0.20013 (16)	0.79252 (15)	0.0432 (5)
N6	0.7001 (2)	0.22903 (18)	0.84909 (16)	0.0526 (6)
O1	−0.08959 (17)	0.84598 (13)	0.26287 (12)	0.0440 (4)
O2	0.49050 (19)	0.65507 (13)	0.58071 (10)	0.0423 (4)
H2B	0.423495	0.670814	0.544597	0.063*
O3	0.51263 (19)	0.84794 (13)	0.59033 (11)	0.0456 (4)
O4	0.7059 (2)	0.94157 (13)	0.69790 (14)	0.0548 (5)
H4A	0.644075	0.938517	0.656275	0.082*
O5	0.81552 (18)	0.50542 (12)	0.81722 (10)	0.0380 (4)
O6	0.58774 (19)	0.37970 (14)	0.74097 (14)	0.0543 (5)
O7	0.0166 (2)	0.14267 (13)	0.41965 (10)	0.0448 (4)
H7	0.080114	0.163181	0.458094	0.067*
O8	−0.0078 (2)	0.33425 (13)	0.41276 (11)	0.0479 (4)
O9	−0.2047 (2)	0.41438 (14)	0.30888 (16)	0.0575 (5)
O10	−0.31118 (18)	−0.03452 (13)	0.18240 (12)	0.0434 (4)
C9A	−0.4007 (9)	0.6164 (8)	0.0684 (6)	0.061 (3)	0.375 (10)
H9AA	−0.456209	0.542674	0.069361	0.074*	0.375 (10)
H9AB	−0.444497	0.674963	0.106875	0.074*	0.375 (10)
C10A	−0.3944 (13)	0.6563 (13)	−0.0178 (11)	0.099 (5)	0.375 (10)
H10D	−0.355335	0.595055	−0.054862	0.149*	0.375 (10)
H10E	−0.331215	0.725178	−0.017286	0.149*	0.375 (10)
H10F	−0.492491	0.67574	−0.039729	0.149*	0.375 (10)
H2A	−0.020 (3)	0.600 (2)	0.2030 (16)	0.044 (7)*
H5B	0.742 (3)	0.460 (3)	0.7997 (19)	0.061 (9)*
H5A	0.526 (4)	0.137 (3)	0.798 (2)	0.075 (10)*
H9	−0.134 (5)	0.409 (4)	0.349 (3)	0.127 (19)*
H10	−0.239 (4)	−0.082 (3)	0.207 (2)	0.088 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0562 (14)	0.0226 (9)	0.0405 (11)	0.0040 (9)	0.0094 (10)	0.0040 (8)
C2	0.0423 (11)	0.0194 (9)	0.0440 (11)	−0.0030 (8)	0.0112 (9)	−0.0006 (8)
C3	0.0279 (9)	0.0205 (8)	0.0426 (11)	0.0002 (7)	0.0084 (8)	−0.0016 (7)
C4	0.0312 (10)	0.0189 (8)	0.0445 (11)	−0.0001 (7)	0.0042 (8)	0.0002 (7)
C5	0.0351 (10)	0.0232 (9)	0.0413 (11)	0.0015 (7)	0.0046 (8)	−0.0025 (8)
C6	0.0260 (9)	0.0240 (9)	0.0542 (12)	0.0000 (7)	0.0027 (8)	−0.0049 (8)
C7	0.079 (2)	0.0343 (13)	0.088 (2)	−0.0137 (13)	−0.0413 (17)	0.0059 (13)
C8	0.082 (2)	0.0470 (15)	0.0618 (17)	−0.0132 (14)	−0.0140 (15)	−0.0107 (13)
C9	0.061 (3)	0.050 (3)	0.049 (3)	−0.003 (2)	−0.015 (2)	−0.002 (2)
C10	0.084 (4)	0.072 (4)	0.061 (3)	0.034 (3)	−0.028 (3)	−0.019 (3)
C11	0.0362 (10)	0.0217 (9)	0.0433 (11)	0.0021 (7)	0.0127 (9)	0.0043 (8)
C12	0.0391 (11)	0.0177 (9)	0.0670 (15)	0.0003 (8)	0.0160 (10)	0.0042 (9)
C13	0.0375 (12)	0.0206 (9)	0.0765 (17)	−0.0053 (8)	0.0063 (11)	−0.0077 (10)
C14	0.0366 (11)	0.0285 (10)	0.0609 (14)	0.0004 (8)	0.0001 (10)	−0.0061 (9)
C15	0.0353 (10)	0.0207 (9)	0.0454 (11)	0.0022 (7)	0.0065 (9)	0.0010 (8)
C16	0.0363 (10)	0.0188 (8)	0.0409 (10)	−0.0005 (7)	0.0085 (8)	0.0002 (7)
C17	0.0461 (12)	0.0264 (10)	0.0420 (11)	0.0065 (8)	0.0156 (9)	0.0077 (8)
C18	0.0384 (11)	0.0240 (9)	0.0521 (13)	−0.0012 (8)	0.0112 (9)	0.0034 (8)
C19	0.0325 (10)	0.0203 (9)	0.0599 (13)	−0.0018 (7)	0.0092 (9)	0.0025 (8)
C20	0.0283 (10)	0.0203 (9)	0.0622 (14)	−0.0010 (7)	0.0111 (9)	0.0056 (8)
C21	0.0371 (11)	0.0210 (9)	0.0670 (15)	0.0033 (8)	0.0162 (10)	0.0031 (9)
C22	0.0515 (14)	0.0219 (9)	0.0568 (14)	−0.0028 (9)	0.0186 (11)	−0.0025 (9)
C23	0.0272 (10)	0.0242 (10)	0.0710 (15)	0.0001 (8)	0.0059 (10)	0.0094 (9)
C24	0.0481 (15)	0.0388 (13)	0.090 (2)	0.0071 (11)	−0.0034 (14)	0.0163 (13)
C25	0.070 (2)	0.0406 (14)	0.095 (2)	−0.0018 (13)	−0.0085 (17)	0.0245 (15)
C26	0.0548 (18)	0.0601 (19)	0.121 (3)	−0.0008 (14)	−0.0222 (18)	0.0203 (19)
C27A	0.073 (3)	0.102 (5)	0.141 (5)	0.020 (3)	−0.035 (3)	−0.012 (4)
C27B	0.123 (16)	0.15 (2)	0.23 (2)	−0.035 (14)	0.033 (15)	0.029 (18)
C28	0.0381 (11)	0.0217 (9)	0.0493 (12)	−0.0007 (8)	0.0181 (9)	−0.0002 (8)
C29	0.0423 (12)	0.0195 (9)	0.0737 (16)	0.0003 (8)	0.0236 (11)	0.0043 (9)
C30	0.0376 (12)	0.0274 (11)	0.0890 (19)	0.0049 (9)	0.0128 (12)	0.0173 (11)
C31	0.0340 (11)	0.0331 (11)	0.0755 (17)	−0.0022 (9)	0.0033 (11)	0.0152 (11)
C32	0.0324 (10)	0.0243 (9)	0.0562 (13)	−0.0017 (8)	0.0072 (9)	0.0035 (9)
C33	0.0339 (10)	0.0210 (9)	0.0488 (12)	0.0001 (7)	0.0114 (9)	0.0022 (8)
C34	0.0510 (13)	0.0240 (9)	0.0446 (12)	−0.0058 (9)	0.0204 (10)	−0.0036 (8)
N1	0.0463 (10)	0.0283 (9)	0.0368 (9)	0.0069 (7)	0.0054 (8)	0.0010 (7)
N2	0.0381 (10)	0.0248 (9)	0.0662 (13)	0.0025 (7)	−0.0114 (9)	−0.0091 (8)
N3	0.0660 (16)	0.0400 (12)	0.119 (2)	0.0099 (11)	−0.0517 (16)	−0.0155 (13)
N4	0.0460 (11)	0.0268 (9)	0.0483 (10)	−0.0054 (7)	0.0136 (8)	−0.0004 (7)
N5	0.0358 (10)	0.0251 (9)	0.0693 (13)	−0.0005 (7)	0.0021 (9)	0.0120 (8)
N6	0.0353 (10)	0.0390 (11)	0.0839 (16)	−0.0011 (8)	−0.0041 (10)	0.0178 (10)
O1	0.0360 (8)	0.0258 (7)	0.0684 (11)	0.0074 (6)	−0.0066 (7)	−0.0091 (7)
O2	0.0569 (10)	0.0297 (8)	0.0402 (8)	0.0081 (7)	−0.0009 (7)	0.0035 (6)
O3	0.0568 (10)	0.0285 (8)	0.0539 (10)	0.0121 (7)	0.0133 (8)	0.0144 (7)
O4	0.0524 (11)	0.0180 (7)	0.0956 (15)	−0.0001 (7)	0.0130 (10)	0.0095 (8)
O5	0.0407 (8)	0.0225 (7)	0.0498 (9)	−0.0005 (6)	−0.0052 (7)	0.0021 (6)
O6	0.0416 (9)	0.0256 (8)	0.0951 (14)	−0.0106 (7)	−0.0117 (9)	0.0181 (8)
O7	0.0642 (11)	0.0259 (7)	0.0438 (9)	−0.0065 (7)	0.0033 (8)	−0.0013 (6)
O8	0.0626 (11)	0.0245 (7)	0.0569 (10)	−0.0098 (7)	0.0181 (8)	−0.0092 (7)
O9	0.0582 (12)	0.0171 (7)	0.0991 (16)	0.0008 (7)	0.0220 (11)	0.0012 (8)
O10	0.0389 (9)	0.0258 (7)	0.0644 (11)	−0.0019 (6)	−0.0071 (8)	0.0010 (7)
C9A	0.052 (5)	0.080 (6)	0.050 (5)	0.005 (4)	−0.005 (4)	−0.025 (4)
C10A	0.073 (7)	0.097 (10)	0.131 (12)	−0.001 (6)	−0.001 (7)	0.059 (9)

Geometric parameters (Å, º) top

C1—N1	1.334 (3)	C22—H22	0.95
C1—C2	1.376 (3)	C23—O6	1.224 (3)
C1—H1	0.95	C23—N5	1.345 (3)
C2—C3	1.390 (3)	C24—N6	1.278 (3)
C2—H2	0.95	C24—C25	1.519 (4)
C3—C4	1.391 (3)	C24—C26	1.526 (4)
C3—C6	1.492 (3)	C25—H25A	0.98
C4—C5	1.379 (3)	C25—H25B	0.98
C4—H4	0.95	C25—H25C	0.98
C5—N1	1.342 (3)	C26—C27B	1.419 (11)
C5—H5	0.95	C26—C27A	1.450 (6)
C6—O1	1.222 (2)	C26—H26A	0.99
C6—N2	1.350 (3)	C26—H26B	0.99
C7—N3	1.268 (4)	C27A—H27A	0.98
C7—C8	1.456 (4)	C27A—H27B	0.98
C7—C9	1.506 (5)	C27A—H27C	0.98
C7—C9A	1.667 (9)	C27B—H27D	0.98
C8—H8A	0.98	C27B—H27E	0.98
C8—H8B	0.98	C27B—H27F	0.98
C8—H8C	0.98	C28—C29	1.397 (3)
C9—C10	1.496 (8)	C28—C33	1.400 (3)
C9—H9A	0.99	C28—C34	1.475 (3)
C9—H9B	0.99	C29—O9	1.365 (3)
C10—H10A	0.98	C29—C30	1.385 (4)
C10—H10B	0.98	C30—C31	1.387 (3)
C10—H10C	0.98	C30—H30	0.95
C11—C12	1.401 (3)	C31—C32	1.391 (3)
C11—C16	1.402 (3)	C31—H31	0.95
C11—C17	1.471 (3)	C32—C33	1.376 (3)
C12—O4	1.363 (2)	C32—O10	1.381 (3)
C12—C13	1.381 (4)	C33—H33	0.95
C13—C14	1.387 (3)	C34—O8	1.241 (2)
C13—H13	0.95	C34—O7	1.303 (3)
C14—C15	1.388 (3)	N2—N3	1.386 (3)
C14—H14	0.95	N2—H2A	0.89 (3)
C15—C16	1.378 (3)	N5—N6	1.391 (3)
C15—O5	1.382 (2)	N5—H5A	0.90 (4)
C16—H16	0.95	O2—H2B	0.84
C17—O3	1.245 (2)	O4—H4A	0.84
C17—O2	1.302 (3)	O5—H5B	0.88 (3)
C18—N4	1.341 (3)	O7—H7	0.84
C18—C19	1.373 (3)	O9—H9	0.88 (5)
C18—H18	0.95	O10—H10	0.95 (4)
C19—C20	1.395 (3)	C9A—C10A	1.446 (18)
C19—H19	0.95	C9A—H9AA	0.99
C20—C21	1.390 (3)	C9A—H9AB	0.99
C20—C23	1.491 (3)	C10A—H10D	0.98
C21—C22	1.371 (4)	C10A—H10E	0.98
C21—H21	0.95	C10A—H10F	0.98
C22—N4	1.334 (3)

N1—C1—C2	122.84 (19)	N5—C23—C20	117.07 (19)
N1—C1—H1	118.6	N6—C24—C25	125.4 (3)
C2—C1—H1	118.6	N6—C24—C26	116.5 (3)
C1—C2—C3	119.01 (19)	C25—C24—C26	118.1 (3)
C1—C2—H2	120.5	C24—C25—H25A	109.5
C3—C2—H2	120.5	C24—C25—H25B	109.5
C2—C3—C4	118.4 (2)	H25A—C25—H25B	109.5
C2—C3—C6	123.74 (18)	C24—C25—H25C	109.5
C4—C3—C6	117.78 (17)	H25A—C25—H25C	109.5
C5—C4—C3	118.75 (18)	H25B—C25—H25C	109.5
C5—C4—H4	120.6	C27B—C26—C24	118.2 (14)
C3—C4—H4	120.6	C27A—C26—C24	113.4 (4)
N1—C5—C4	122.76 (19)	C27A—C26—H26A	108.9
N1—C5—H5	118.6	C24—C26—H26A	108.9
C4—C5—H5	118.6	C27A—C26—H26B	108.9
O1—C6—N2	123.0 (2)	C24—C26—H26B	108.9
O1—C6—C3	120.31 (19)	H26A—C26—H26B	107.7
N2—C6—C3	116.69 (18)	C26—C27A—H27A	109.5
N3—C7—C8	126.1 (3)	C26—C27A—H27B	109.5
N3—C7—C9	121.6 (3)	H27A—C27A—H27B	109.5
C8—C7—C9	111.3 (3)	C26—C27A—H27C	109.5
N3—C7—C9A	105.9 (4)	H27A—C27A—H27C	109.5
C8—C7—C9A	123.6 (4)	H27B—C27A—H27C	109.5
C7—C8—H8A	109.5	C26—C27B—H27D	109.5
C7—C8—H8B	109.5	C26—C27B—H27E	109.5
H8A—C8—H8B	109.5	H27D—C27B—H27E	109.5
C7—C8—H8C	109.5	C26—C27B—H27F	109.5
H8A—C8—H8C	109.5	H27D—C27B—H27F	109.5
H8B—C8—H8C	109.5	H27E—C27B—H27F	109.5
C10—C9—C7	115.1 (4)	C29—C28—C33	119.6 (2)
C10—C9—H9A	108.5	C29—C28—C34	120.31 (19)
C7—C9—H9A	108.5	C33—C28—C34	120.1 (2)
C10—C9—H9B	108.5	O9—C29—C30	119.1 (2)
C7—C9—H9B	108.5	O9—C29—C28	121.5 (2)
H9A—C9—H9B	107.5	C30—C29—C28	119.4 (2)
C9—C10—H10A	109.5	C29—C30—C31	120.6 (2)
C9—C10—H10B	109.5	C29—C30—H30	119.7
H10A—C10—H10B	109.5	C31—C30—H30	119.7
C9—C10—H10C	109.5	C30—C31—C32	120.1 (2)
H10A—C10—H10C	109.5	C30—C31—H31	119.9
H10B—C10—H10C	109.5	C32—C31—H31	119.9
C12—C11—C16	119.4 (2)	C33—C32—O10	122.89 (19)
C12—C11—C17	120.30 (18)	C33—C32—C31	119.7 (2)
C16—C11—C17	120.32 (19)	O10—C32—C31	117.4 (2)
O4—C12—C13	119.1 (2)	C32—C33—C28	120.5 (2)
O4—C12—C11	121.4 (2)	C32—C33—H33	119.7
C13—C12—C11	119.49 (19)	C28—C33—H33	119.7
C12—C13—C14	120.6 (2)	O8—C34—O7	122.9 (2)
C12—C13—H13	119.7	O8—C34—C28	121.6 (2)
C14—C13—H13	119.7	O7—C34—C28	115.43 (18)
C13—C14—C15	120.3 (2)	C1—N1—C5	118.24 (19)
C13—C14—H14	119.8	C6—N2—N3	118.15 (19)
C15—C14—H14	119.8	C6—N2—H2A	119.9 (17)
C16—C15—O5	122.69 (18)	N3—N2—H2A	121.0 (17)
C16—C15—C14	119.58 (19)	C7—N3—N2	117.1 (2)
O5—C15—C14	117.7 (2)	C22—N4—C18	118.3 (2)
C15—C16—C11	120.56 (19)	C23—N5—N6	117.11 (19)
C15—C16—H16	119.7	C23—N5—H5A	120 (2)
C11—C16—H16	119.7	N6—N5—H5A	122 (2)
O3—C17—O2	122.6 (2)	C24—N6—N5	116.7 (2)
O3—C17—C11	122.0 (2)	C17—O2—H2B	109.5
O2—C17—C11	115.34 (17)	C12—O4—H4A	109.5
N4—C18—C19	122.9 (2)	C15—O5—H5B	106 (2)
N4—C18—H18	118.6	C34—O7—H7	109.5
C19—C18—H18	118.6	C29—O9—H9	103 (3)
C18—C19—C20	118.57 (19)	C32—O10—H10	106 (2)
C18—C19—H19	120.7	C10A—C9A—C7	101.5 (8)
C20—C19—H19	120.7	C10A—C9A—H9AA	111.5
C21—C20—C19	118.4 (2)	C7—C9A—H9AA	111.5
C21—C20—C23	123.8 (2)	C10A—C9A—H9AB	111.5
C19—C20—C23	117.71 (18)	C7—C9A—H9AB	111.5
C22—C21—C20	119.0 (2)	H9AA—C9A—H9AB	109.3
C22—C21—H21	120.5	C9A—C10A—H10D	109.5
C20—C21—H21	120.5	C9A—C10A—H10E	109.5
N4—C22—C21	122.9 (2)	H10D—C10A—H10E	109.5
N4—C22—H22	118.6	C9A—C10A—H10F	109.5
C21—C22—H22	118.6	H10D—C10A—H10F	109.5
O6—C23—N5	123.0 (2)	H10E—C10A—H10F	109.5
O6—C23—C20	119.9 (2)

N1—C1—C2—C3	−0.1 (3)	N6—C24—C26—C27B	−39.4 (16)
C1—C2—C3—C4	−0.9 (3)	C25—C24—C26—C27B	141.7 (16)
C1—C2—C3—C6	−177.54 (19)	N6—C24—C26—C27A	−112.4 (5)
C2—C3—C4—C5	1.4 (3)	C25—C24—C26—C27A	68.7 (5)
C6—C3—C4—C5	178.25 (18)	C33—C28—C29—O9	−177.8 (2)
C3—C4—C5—N1	−1.0 (3)	C34—C28—C29—O9	1.3 (3)
C2—C3—C6—O1	153.6 (2)	C33—C28—C29—C30	2.5 (3)
C4—C3—C6—O1	−23.1 (3)	C34—C28—C29—C30	−178.4 (2)
C2—C3—C6—N2	−25.0 (3)	O9—C29—C30—C31	177.7 (2)
C4—C3—C6—N2	158.3 (2)	C28—C29—C30—C31	−2.6 (4)
N3—C7—C9—C10	4.3 (7)	C29—C30—C31—C32	0.8 (4)
C8—C7—C9—C10	−164.9 (5)	C30—C31—C32—C33	1.2 (4)
C16—C11—C12—O4	−177.7 (2)	C30—C31—C32—O10	−179.0 (2)
C17—C11—C12—O4	1.4 (3)	O10—C32—C33—C28	178.92 (19)
C16—C11—C12—C13	2.2 (3)	C31—C32—C33—C28	−1.2 (3)
C17—C11—C12—C13	−178.6 (2)	C29—C28—C33—C32	−0.6 (3)
O4—C12—C13—C14	177.7 (2)	C34—C28—C33—C32	−179.67 (19)
C11—C12—C13—C14	−2.3 (4)	C29—C28—C34—O8	−4.4 (3)
C12—C13—C14—C15	0.2 (4)	C33—C28—C34—O8	174.6 (2)
C13—C14—C15—C16	1.8 (3)	C29—C28—C34—O7	174.84 (19)
C13—C14—C15—O5	−178.7 (2)	C33—C28—C34—O7	−6.1 (3)
O5—C15—C16—C11	178.74 (18)	C2—C1—N1—C5	0.5 (3)
C14—C15—C16—C11	−1.8 (3)	C4—C5—N1—C1	0.0 (3)
C12—C11—C16—C15	−0.2 (3)	O1—C6—N2—N3	−2.9 (4)
C17—C11—C16—C15	−179.35 (19)	C3—C6—N2—N3	175.6 (2)
C12—C11—C17—O3	−4.1 (3)	C8—C7—N3—N2	−4.9 (6)
C16—C11—C17—O3	175.05 (19)	C9—C7—N3—N2	−172.5 (4)
C12—C11—C17—O2	175.17 (19)	C9A—C7—N3—N2	152.1 (5)
C16—C11—C17—O2	−5.7 (3)	C6—N2—N3—C7	179.9 (3)
N4—C18—C19—C20	−0.7 (3)	C21—C22—N4—C18	0.4 (3)
C18—C19—C20—C21	1.0 (3)	C19—C18—N4—C22	0.0 (3)
C18—C19—C20—C23	177.6 (2)	O6—C23—N5—N6	−5.6 (4)
C19—C20—C21—C22	−0.7 (3)	C20—C23—N5—N6	173.0 (2)
C23—C20—C21—C22	−177.1 (2)	C25—C24—N6—N5	−2.7 (5)
C20—C21—C22—N4	0.0 (3)	C26—C24—N6—N5	178.5 (3)
C21—C20—C23—O6	155.2 (2)	C23—N5—N6—C24	173.4 (3)
C19—C20—C23—O6	−21.2 (3)	N3—C7—C9A—C10A	106.4 (9)
C21—C20—C23—N5	−23.4 (3)	C8—C7—C9A—C10A	−95.9 (9)
C19—C20—C23—N5	160.2 (2)

Cocrystals of izact and izbt that share the same coformer. The crystal structure similarity tool of Mercury (Macrae et al., 2020) was used to help determine if related structures were isostructural top

Coformer	izact refcode	izbt refcode	Isostructural
4-tert-Butylbenzoic acid	GIYMAF	GIYMEJ	Yes
2-Hydroxybenzoic acid (salicylic acid)*	LATLAV	UBILAW	No
3-Hydroxybenzoic acid (anhydrous)	FADHUP	FADHOJ	No
3-Hydroxybenzoic acid hydrate	SAYPIT	SAYPOZ	Yes
4-Nitrobenzoic acid	XOPYEJ	XOPYUZ	Yes

Note: (*) it should be noted that the unit-cell parameters of both structures are similar but the orientation of the molecules with respect to the unit cells differ significantly.

Onset temperatures and associated enthalpies for the DSC curves of the cocrystals presented in this work, as well as the melting points and entahlpies of some of the comparison cocrystals top

Thermal event	Onset (°C)	Enthalpy (J g^-1)	Enthalpy (kJ mol^-1)
izact–1-nta melting/decomposition	106.1 ± 0.5	170.9 ± 5.2	59.7 ± 2
izbt–1-nta melting/decomposition	89.5± 0.1	167.8± 2.5	61.0 ± 1
izbt–2c4n melting/decomposition	102.1 ± 0.2	100.6 ± 2.3	39.5 ± 1
izbt–2,4-dhba melting/decomposition	174.8± 0.2	226.3 ± 4.3	78.2 ± 1
izbt–2,5-dhba melting/decomposition	151.2 ± 0.2	132.5 ± 3.2	45.8 ± 1
izact m.p. (Lemmerer, 2012)	160.0	–	29.7
izact–2c4n m.p. (Lemmerer, 2012)	93.4	–	33.4

Acknowledgements

The authors acknowledge and thank the DSI/NRF Centre of Excellence in Strong Materials, as well as the NRF, for funding the Bruker D2 Phaser diffractometer.

References

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STRUCTURAL
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ISSN: 2053-2296

Volume 79| Part 9| September 2023| Pages 365-373

https://doi.org/10.1107/S2053229623007179

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